JP4658070B2 - Modified phenolic resin, epoxy resin composition containing the same, and prepreg using the same - Google Patents

Description

The present invention relates to a modified phenolic resin and a method for producing the same, and an epoxy resin composition using the modified phenolic resin and a cured product thereof. More specifically, the present invention relates to a modified phenolic resin used for insulating materials for electrical and electronic parts including a curing agent for epoxy resin for semiconductor encapsulation, and laminated boards such as printed wiring boards, adhesives, molding materials, paints and the like.
The present invention also relates to a prepreg, a laminate and an electronic circuit board using an epoxy resin composition. More specifically, a glass substrate is impregnated with an epoxy resin composition comprising an epoxy compound or epoxy resin, a curing agent comprising a modified phenolic resin, and a curing accelerator and having improved heat resistance, flame retardancy, and adhesion. The present invention relates to a prepared prepreg, a laminate obtained by laminating the prepreg, and an electronic circuit board using the laminate.

Phenolic resin is a compound useful as a curing agent for epoxy resin for semiconductor encapsulation, raw materials for epoxy resin, adhesives, molding materials, and paints, and has excellent electrical properties, heat resistance, adhesion, moisture resistance, etc. Is widely used in fields such as electrical and electronic parts, structural materials, adhesives and paints.
In addition, along with the development of the electrical and electronic fields, epoxy resins for semiconductor encapsulation have high purity, heat resistance, moisture resistance, adhesion, low viscosity, high dielectric properties, and fast curing for high filler filling. Various properties such as properties and flame retardancy are required. In particular, due to the use of lead-free solder due to environmental problems, the soldering process becomes hotter than before, and in order to prevent peeling and cracking of the package, chips and frames that are IC components and sealing resin, or There is a demand for improved adhesion characteristics between the filler and the sealing material resin.

Moreover, the improvement of the flame retardance characteristic of resin itself is calculated | required from the use regulation of the brominated flame retardant currently used.
In order to solve these problems, Japanese Patent Application Laid-Open No. 2003-286392 improves the adhesion by adding dibenzothiophene to the epoxy composition, and cracks generated in the package during heating in the solder reflow process. Deterrence techniques are shown. However, this compound is extremely poor in reactivity and has a low boiling point of around 330 ° C., which causes problems in heat resistance and flame retardancy.

  Japanese Patent Application Laid-Open No. 10-237060 discloses a technique in which polyhydric phenols obtained by polycondensation of hetero compound aldehydes and phenols improve adhesion to prevent peeling of the package. . However, in the production of these polyhydric phenols, the reactivity is very low, so the reaction time is long and it is difficult to polymerize. There are many processes such as neutralization of alkaline water and repeated washing of the generated salt, and the amount of neutralized water and washing water is large. In addition, the molded article has a number of problems such as a slow curing speed and a decrease in mechanical strength.

  Moreover, a phenol resin is a useful compound as a curing agent for an epoxy resin for an electronic circuit board, a raw material for the epoxy resin, or the like. The cured product has excellent electrical properties, heat resistance, adhesiveness, moisture resistance, etc., and a fiber reinforced resin board made by impregnating and curing a phenol resin into a fiber base material, for example, a fiber reinforced resin laminate, is electrically insulated. Widely used in the field of electrical and electronic parts such as materials.

A fiber reinforced resin plate with phenol resin as a matrix is prepared by impregnating and drying a phenol resin varnish in which a phenol resin is dissolved in an organic solvent to prepare a prepreg as a semi-curing stage, and laminating a predetermined number of the prepregs. Then, it can be produced by completely curing the resin.
Examples of phenolic resins used in the production of such fiber reinforced resin plates include resol type phenol resins. Fiber reinforced resin plates using resol type phenol resins have low electrical insulation and poor heat resistance. There was a drawback of being sufficient. In order to solve these drawbacks, Japanese Patent Laid-Open No. 73824 proposes a fiber reinforced resin plate using various novolac type phenol resins as a matrix. However, the flame retardancy is insufficient, and it is necessary to add a brominated flame retardant to impart flame retardancy to the resin composition.

In addition, brominated flame retardants that have been used in the past are also restricted in use by EU regulations, and there is a demand for improving the flame retardant properties of the resin itself.
On the other hand, the multilayer printed circuit board manufacturing method is a multi-layer wiring by so-called build-up method in which organic insulating films are alternately laminated on the conductor layer without using glass cloth which is disadvantageous for dielectric properties instead of the conventional laminating press. Plate development is actively underway.

In the build-up method, a rubber component may be added to improve the adhesion between the insulating layer and the conductor layer, but since the rubber component remains in the insulating layer, characteristics such as heat resistance and electrical insulation properties are degraded. It may be a cause. Therefore, improvement of the adhesion property of the resin itself is required.

  The present invention relates to an insulating material for electrical and electronic parts such as a semiconductor sealing material, and an epoxy having excellent adhesion and flame retardancy in applications such as laminates such as printed wiring boards, adhesives, molding materials and paints. An object of the present invention is to provide a modified phenolic resin capable of providing a resin, a method for producing the modified phenolic resin, and an epoxy resin composition using the phenolic resin as a curing agent.

In addition, the present invention uses an epoxy resin composition that uses a specific modified phenolic resin as a curing agent and has improved heat resistance, flame retardancy, and adhesion in addition to electrical insulation required as an electrical / electronic material. An object of the present invention is to provide a prepreg obtained by impregnating a glass substrate with a glass substrate, a laminate, and an electronic circuit board.

  As a result of intensive studies to achieve the above object, the present inventors have found that a compound represented by the general formula (6-1) in an aromatic ring having a hydroxyl group of a phenol resin in the presence of an acid catalyst.

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. B represents a hydroxyl group or a halogen atom.)
Is a novel modified phenolic resin that can provide an epoxy resin with good adhesion and flame retardancy in applications such as insulating materials for electrical and electronic parts, laminates, adhesives, molding materials, paints, etc. As a result, the present invention has been completed.

That is, the modified phenolic resin according to the present invention is [1] a hydroxyl group of a phenolic resin which is an alternating copolymer of at least one phenolic compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group. A group represented by the general formula (1-1) is introduced as a side chain of an aromatic ring having a characteristic.

(In the formula, R ¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms.)
[2] A sulfur atom is contained in an amount of 0.01 to 2 mol with respect to 1 mol of the hydroxyl group of the modified phenol resin according to [1].
[3] The modified phenolic resin according to [1] or [2] is represented by the general formula (2-1).

(In the formula, R ¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms.
R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, a linear or branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms, and may be the same or different. The linking group A represents a hydrocarbon group having 1 to 20 carbon atoms. k, o, x and z are integers of 0 to 4, m and y are integers of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. Moreover, the repeating unit number n shows the integer of 0-50. )
[4] The modified phenolic resin according to [1] or [2] is represented by the general formula (3-1).

(In the formula, R ¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms.
R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, a linear or branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms, and may be the same or different. The linking group A represents a hydrocarbon group having 1 to 20 carbon atoms. k, o, x and z are integers of 0 to 6, m and y are integers of 0 to 5, and the total number of x, y and z is an integer of 1 to 17. Moreover, the repeating unit number n shows the integer of 0-50. )
[5] The linking group A of the modified phenol resin described in [3] or [4] is at least one selected from a methylene group, a xylylene group, a biphenylaralkyl group, and a group represented by the general formula (4-1). It is characterized by being.

[6] The method for producing the modified phenolic resin represented by the general formula (2-1) includes a phenol resin represented by the general formula (5-1) and a compound represented by the general formula (6-1). The reaction is carried out in the presence of an acid catalyst.

(Wherein R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, a linear or branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms, and may be the same or different. The linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k and o are integers of 0 to 4, m is an integer of 0 to 3, and the number of repeating units n is an integer of 0 to 50. .)

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. B represents a hydroxyl group or a halogen atom.)
[7] The method for producing the modified phenolic resin represented by the general formula (3-1) includes a phenol resin represented by the general formula (7-1) and a compound represented by the general formula (6-1). The reaction is carried out in the presence of an acid catalyst.

(Wherein R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, a linear or branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms, and may be the same or different. The linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k and o are integers of 0 to 6, m is an integer of 0 to 5, and the number of repeating units n is an integer of 0 to 50. .)

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. B represents a hydroxyl group or a halogen atom.)
[8] In the method for producing a modified phenol resin according to [6] or [7], the linking group A is selected from a methylene group, a xylylene group, a biphenylaralkyl group, and a group represented by the general formula (4). It is at least one kind.

[9] The epoxy resin composition according to the present invention comprises (A) a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin, (B) a curing agent, and (C) a curing accelerator. The (B) curing agent is the modified phenolic resin according to any one of [1] to [5].
[10] The epoxy resin composition according to [9], wherein (D) an organic and / or inorganic filler comprises (A) a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin and (B) a curing agent. It is contained in the range of 100-1900 mass parts with respect to the total mass of 100 mass parts.
[11] The cured epoxy resin according to the present invention is obtained by thermosetting the epoxy resin composition according to any one of [9] or [10].
Moreover, the prepreg which impregnated the epoxy resin composition of this invention to the glass base material, the laminated board formed by laminating it, and an electronic circuit board using the same are provided by the description matter below.
[1] A prepreg according to the present invention is an epoxy resin composition comprising (A) a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin, (B) a curing agent, and (C) a curing accelerator. The (B) curing agent is a phenol resin which is an alternating copolymer of at least one phenol compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group, and has a hydroxyl group. A modified phenolic resin into which a group represented by the general formula (1-1) is introduced as a side chain of the ring, wherein the epoxy resin composition is impregnated in a glass substrate.

(In the formula, R ¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms.)
[2] In the prepreg according to [1] above, (B) the curing agent is an alternating copolymer of at least one phenol compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group. It is a certain phenol resin and is a modified phenol resin into which a group represented by the general formula (1-2) is introduced as a side chain of an aromatic ring having a hydroxyl group.

(In the formula, R ¹ represents an alkylene group having 1 to 3 carbon atoms, a 1,4-cyclohexylene group, or a phenylene group.)
[3] The prepreg according to [1] above, wherein the (B) curing agent is a modified phenol resin represented by the general formula (2-2).

(In the formula, R ¹ represents an alkylene group having 1 to 3 carbon atoms, 1,4-cyclohexylene group, or phenylene group. R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a hydroxyl group, a phenyl group, Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which may be the same or different, and the linking group A is an alkylene group having 1 to 3 carbon atoms, a carbon atom; Represents a divalent group, a phenylene group, a xylylene group, or a biphenylaralkyl group of an alicyclic hydrocarbon of 6 to 12. k, o, x, and z are integers of 0 to 4, and m and y are 0 to 3 And the total number of x, y and z each represents an integer of 1 to 11. The number of repeating units n represents an integer of 0 to 50.)
[4] The prepreg according to [1], wherein the (B) curing agent is a modified phenol resin represented by the general formula (3-2).

(Wherein R ¹ , R ² , linking group A, k, o, x, z, m, y, and the number of repeating units n are
Same as above. )
[5] In the prepreg according to the above [3] or [4], the linking group A is at least one selected from a methylene group, a xylylene group, a biphenylaralkyl group, or a group represented by the general formula (4-1). It is characterized by being a modified phenolic resin.

[6] The prepreg according to any one of [1] to [5] is characterized in that a glass substrate is impregnated with an epoxy resin composition having an epoxy equivalent of 170 to 1000 g / eq.
[7] In the prepreg according to any one of [1] to [6], (A) the bifunctional or higher functional epoxy compound or the bifunctional or higher functional epoxy resin is 100 parts by weight of the (B) curing agent. A glass substrate is impregnated with 150 parts by weight of an epoxy resin composition.
[8] A laminated board according to the present invention is formed by laminating the prepreg according to any one of the above [1] to [7].
[9] An electronic circuit board according to the present invention is characterized by using the laminated board according to the above [8].

The modified phenolic resin of the present invention can exhibit excellent adhesion and flame retardancy when used as a curing agent for epoxy resins, and is extremely valuable industrially.
Further, by using the modified phenolic resin of the present invention as an epoxy resin curing agent, an epoxy resin composition having improved heat resistance, flame retardancy, and adhesion in addition to electrical insulation required for electrical and electronic materials It is possible to provide a prepreg obtained by impregnating a glass substrate with a product, a laminate obtained by laminating the prepreg, and an electronic circuit board using the prepreg.

Hereinafter, the modified phenolic resin according to the present invention, the production method thereof, the epoxy resin composition containing the modified phenolic resin as a curing agent, and the cured product thereof will be specifically described.
[Modified phenolic resin of the present invention]
The modified phenolic resin of the present invention is a phenolic resin which is an alternating copolymer of at least one phenolic compound selected from phenol, naphthol and derivatives thereof (hereinafter referred to as a phenolic compound) and a compound having a divalent linking group. This is a modified phenolic resin having a structure in which a group represented by the general formula (1-1) is introduced as a side chain of an aromatic ring having a hydroxyl group.

(In the formula, R ¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms.)
Specific examples of R ¹ of the group represented by the general formula (1) include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, ethylethylene, 2-methyl- Tetramethylene, 2-methyl-hexamethylene, 2-ethyl-hexamethylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cyclooctylene, vinylene, propenylene , Butanediylidene, 1-propanyl-3-ylidene, o-phenylene, m-phenylene, p-phenylene, 3-cyclohexene-1,2-ylene, 2,5-cyclohexadiene-1,4-ylene, etc. Of these, methylene and ethylene are particularly preferred.

The modified phenolic resin of the present invention has a sulfur atom of 0.01 to 2 mol, preferably 0.05 to 1.5 mol, more preferably 0.1 to 1 mol, per 1 mol of hydroxyl group of the modified phenolic resin. It is preferable to include.
The hydroxyl group content in the modified phenolic resin is determined by, for example, acetylating with acetic anhydride using pyridine as a solvent and titrating the acetic acid produced after decomposing the excess reagent with water with a potassium hydroxide solution. The sulfur atom content can be determined by a method such as NMR analysis in a chloroform solvent.

  Examples of such a modified phenolic resin include compounds represented by the following general formula (2-1).

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, or a linear chain having 1 to 10 carbon atoms. Or a branched or cyclic alkyl group or alkoxy group, which may be the same or different, the linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k, o, x and z are 0; (The integer of -4, m, and y show the integer of 0-3, the total number of x, y, and z shows the integer of 1-11. Moreover, the repeating unit number n shows the integer of 0-50.)
Moreover, the compound represented by the following general formula (3-1) can be mentioned.

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, or a linear chain having 1 to 10 carbon atoms. Or a branched or cyclic alkyl group or alkoxy group, which may be the same or different, the linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k, o, x and z are 0; The integer of -6, m, and y show the integer of 0-5, the total number of x, y, and z shows the integer of 1-17, and the repeating unit number n shows the integer of 0-50.)
Examples of the modified phenolic resin as described above include, in general formula (2-1) or general formula (3-1), as R ¹ , specifically, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, Heptamethylene, octamethylene, ethylethylene, 2-methyl-tetramethylene, 2-methyl-hexamethylene, 2-ethyl-hexamethylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexene Silene, 1,4-cyclooctylene, vinylene, propenylene, butanediylidene, 1-propanyl-3-ylidene, o-phenylene, m-phenylene, p-phenylene, 3-cyclohexene-1,2-ylene, 2,5- Examples include cyclohexadiene-1,4-ylene, and among these, methylene and ethylene are particularly preferable.

Specific examples of R ² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, isopentyl, isohexyl, neopentyl, tert-butyl, tert-pentyl, cyclopropyl, And cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, methoxy, ethoxy, propoxy, butoxy, phenoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, phenyl, naphthyl, antil, phenanthyl, etc. In particular, a hydrogen atom, a halogen atom, a hydroxyl group, methyl, and methoxy are preferable.

  The linking group A may be a divalent compound. Specifically, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, general formula (4 -1), 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cyclooctylene, vinylene, propenylene, butanediylidene, 1-propanyl-3-ylidene, o-phenylene, m -Phenylene, p-phenylene, 3-cyclohexene-1,2-ylene, 2,5-cyclohexadiene-1,4-ylene, 1,2-xylylene, 1,3-xylylene, 1,4-xylylene, 1, Examples include 2-xylylene-biphenyl, 1,3-xylylene-biphenyl, and 1,4-xylylene-biphenyl. In order to obtain good adhesion and flame retardancy, the linking group A is especially methylene, 1,2-xylylene, 1,3-xylylene, 1,4-xylylene, 1,2-xylylene. -Biphenyl, 1,3-xylylene-biphenyl, 1,4-xylylene-biphenyl, and groups represented by general formula (4-1) are preferred.

  In the general formula (2-1), x and z are integers of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and y is an integer of 0 to 3, preferably It is preferably an integer of 0 to 2, more preferably an integer of 0 to 1. The total number of x, y and z is preferably an integer of 1 to 11, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. The number of repeating units n is preferably an integer of 0-50, more preferably an integer of 0-15.

  In general formula (3-1), x and z are integers of 0 to 6, preferably 0 to 3, more preferably 0 to 1, and y is an integer of 0 to 5, preferably It is preferably an integer of 0 to 2, more preferably an integer of 0 to 1. The total number of x, y and z is preferably an integer of 1 to 17, preferably an integer of 1 to 10, and more preferably an integer of 1 to 3. The number of repeating units n is preferably an integer of 0-50, more preferably an integer of 0-15.

In addition, the modified phenolic resin of the present invention is a group represented by the general formula (1-1) as a side chain of an aromatic ring having a hydroxyl group.

(In the formula, R ¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms.) By introducing a specific structure, conventional phenol novolac resins and phenol aralkyl resins are introduced . The mechanical properties such as curability, glass transition temperature, hygroscopicity, bending strength, etc. possessed by the present invention can be greatly improved without adversely affecting the performance of adhesion and flame retardancy. Depending on the structure of the phenolic resin, the durable moisture resistance time is 100 to 130 hours for the modified phenol novolak resin of the present invention, 100 to 148 hours for the modified phenol dicyclopentadiene resin of the present invention, and 300 for the modified phenol aralkyl resin of the present invention. It is preferably ˜408 hours, 300 to 408 hours for the modified phenol biphenyl aralkyl resin of the present invention, and 300 to 374 hours for the modified naphthol aralkyl resin of the present invention. The flame retardancy is preferably V-1 and further V-0 according to UL94 test evaluation criteria.

Specific examples of the modified phenol resin having a specific structure represented by the general formula (2-1) or the general formula (3-1) of the present invention are shown in the following chemical formulas (1) to (20).
Chemical formula (1).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (2).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (3).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (4).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (5).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (6).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (7).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (8).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (9).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (10).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (11).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (12).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (13).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (14).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (15).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (16).

(In the formula, x and z are integers of 0 to 4, y is an integer of 0 to 3, and the total number of x, y and z is an integer of 1 to 11. The number of repeating units n is 0 to 0. Indicates an integer of 50.)
Chemical formula (17).

(In the formula, x and z are integers of 0 to 6, y is an integer of 0 to 5, and the total number of x, y and z is an integer of 1 to 17. The number of repeating units n is 0 to 0. It represents an integer of 50.) Further, the hydroxyl group and the group represented by the general formula (1) may be substituted at any position of the naphthalene ring.
Chemical formula (18).

(In the formula, x and z are integers of 0 to 6, y is an integer of 0 to 5, and the total number of x, y and z is an integer of 1 to 17. The number of repeating units n is 0 to 0. It represents an integer of 50.) Further, the hydroxyl group and the group represented by the hydroxyl group and the general formula (1-1) may be substituted at any position of the naphthalene ring.
Chemical formula (19).

(In the formula, x and z are integers of 0 to 6, y is an integer of 0 to 5, and the total number of x, y and z is an integer of 1 to 17. The number of repeating units n is 0 to 0. It represents an integer of 50.) Further, the hydroxyl group and the group represented by the general formula (1-1) may be substituted at any position of the naphthalene ring.
Chemical formula (20).

(In the formula, x and z are integers of 0 to 6, y is an integer of 0 to 5, and the total number of x, y and z is an integer of 1 to 17. The number of repeating units n is 0 to 0. It represents an integer of 50.) Further, the hydroxyl group and the group represented by the general formula (1-1) may be substituted at any position of the naphthalene ring.
Among the modified phenol novolak resins, modified phenol dicyclopentadiene resins, modified phenol aralkyl resins, modified phenol biphenyl aralkyl resins and modified naphthol aralkyl resins represented by the above chemical formulas (1) to (20), the chemical formula (1), Compounds represented by chemical formula (2), chemical formula (5), chemical formula (6), chemical formula (9), chemical formula (10), chemical formula (13), chemical formula (14), chemical formula (17) and chemical formula (18) are: It is preferable because it has particularly excellent adhesion and flame retardancy.
[Method for producing modified phenolic resin of the present invention]
The modified phenol resin of the present invention is an aromatic ring having a hydroxyl group of a phenol resin that is an alternating copolymer of at least one phenol compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group. The side chain has a structure in which a group represented by the general formula (1-1) is introduced. The phenol resin and the compound represented by the general formula (6-1) It can be obtained by reacting in the presence.

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. B represents a hydroxyl group or a halogen atom.)
The modified phenol resin represented by the general formula (2-2), which is the modified phenol resin of the present invention, is composed of at least one phenol compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group. As a phenol resin which is an alternating copolymer, a phenol resin represented by the following general formula (5-1);

(Wherein R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, a linear or branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms, and may be the same or different. The linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k and o are integers of 0 to 4, m is an integer of 0 to 3, and the number of repeating units n is an integer of 0 to 50. .) It can be obtained by reacting the compound represented by the general formula (6-1) in the presence of an acid catalyst.

(In the formula, R ² represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. B represents a hydroxyl group or a halogen atom.)
The modified phenolic resin represented by the general formula (3-1) is a phenol that is an alternating copolymer of at least one phenol compound selected from phenol, naphthol, and derivatives thereof and a compound having a divalent linking group. As the resin, specifically, a phenol resin represented by the following general formula (7-1);

(Wherein R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, a linear or branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms, and may be the same or different. The linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k and o are integers of 0 to 6, m is an integer of 0 to 5, and the number of repeating units n is an integer of 0 to 50. .) It can be obtained by reacting the compound represented by the general formula (6) in the presence of an acid catalyst.

(In the formula, R ² represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. B represents a hydroxyl group or a halogen atom.)
Specific examples of the phenol resin represented by the general formula (5-1) of the present invention include a phenol novolak resin, a phenol-dicyclopentadiene resin, a phenol aralkyl resin, a phenol biphenyl aralkyl resin, and a general formula (7-1). Examples of the phenol resin represented by the formula include naphthol aralkyl resin and the like, and may be used alone or in combination of two or more phenol resins.

  As the phenol resin represented by the general formula (5-1) or the general formula (7-1) of the present invention, a phenol novolac resin is obtained by reacting a phenol compound and formaldehyde in the presence of an acid catalyst. Examples of the phenol compound used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, and p-ethylphenol.

 The phenol-dicyclopentadiene resin is obtained by reacting a phenol compound with dicyclopentadiene. Examples of the phenol compound used include phenol, o-cresol, m-cresol, p-cresol, and o-ethylphenol. , M-ethylphenol, p-ethylphenol, pn-propylphenol, p-isopropylphenol, pn-butylphenol, p-sec-butylphenol, p-tert-butylphenol, octylphenol, nonylphenol, p-cyclohexylphenol, 2,4-xylenol, 2,6-xylenol, 4,6-xylenol, 3,5-xylenol, 2,4,6-trimethylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, o- Phenylpheno M-phenylphenol, p-phenylphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-fluorophenol, m-fluorophenol, p-fluorophenol, o-iodophenol, m-iodo Phenol, p-iodophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-dihydroxybenzene, m-dihydroxybenzene, p-dihydroxybenzene, and the like. You may use together.

  The phenol aralkyl resin is obtained by reacting a phenol compound with an aralkyl compound which is an aralkyl halide, aralkyl alcohol or a derivative thereof. Examples of the phenol compound to be used include those similar to those of the above-mentioned phenol-dicyclopentadiene resin. Aralkyl compounds to be reacted with phenolic compounds include α, α'-dichloro-p-xylene, α, α'-dichloro-m-xylene, α, α'-dichloro-o-xylene, α, α'-dibromo-p Α, α'-dihaloxylenes such as -xylene, α, α'-dibromo-m-xylene, α, α'-dibromo-o-xylene; α, α'-dihydroxy-p-xylene, α, α '-Dihydroxy-m-xylene, α, α'-dihydroxy-o-xylene xylylene glycols; α, α'-dimethoxy-p-xylene, α, α'-dimethoxy-m-xylene, α, α' -Dimethoxy-o-xylene, α, α'-diethoxy-p-xylene, α, α'-diethoxy-m-xylene, α, α'-diethoxy-o-xylene, α, α'-dipropoxy-p-xylene Α, α′-dipropoxy-m-xylene, α, α′-dipropoxy-o-xylene, α, α′-diisopropoxy-p-xylene , Α, α'-diisopropoxy-m-xylene, α, α'-diisopropoxy-o-xylene, α, α'-di-tert-butoxy-p-xylene, α, α'-di-tert -Butoxy-m-xylene, α, α'-di-tert-butoxy-m-xylene, α, α'-di-n-butoxy-p-xylene, α, α'-di-n-butoxy-m- Examples include α, α′-dialkoxyxylenes such as xylene and α, α′-di-n-butoxy-o-xylene, and two or more aralkyl compounds may be used in combination.

  The phenol biphenyl aralkyl resin is obtained by reacting a phenol compound with a biphenyl aralkyl halide or a biphenyl aralkyl compound that is a derivative thereof. Examples of the phenol compound to be used include those similar to those of the above-mentioned phenol-dicyclopentadiene resin. Examples of the biphenyl aralkyl compound to be reacted with the phenol compound include 2,2′-bischloromethyl biphenyl, 2,3′-bischloromethyl biphenyl, 2,4′-bischloromethyl biphenyl, 3,3′-bischloromethyl biphenyl, 3,4′-bischloromethylbiphenyl, 4,4′-bischloromethylbiphenyl, 2,2′-bisbromomethylbiphenyl, 2,3′-bisbromomethylbiphenyl, 2,4′-bisbromomethylbiphenyl, Examples include, but are not limited to, dihalogenomethylbiphenyls such as 3,3′-bisbromomethylbiphenyl, 3,4′-bisbromomethylbiphenyl, and 4,4′-bisbromomethylbiphenyl. A single compound or two or more biphenyl aralkyl compounds may be used in combination.

The naphthol aralkyl resin can be obtained by reacting with aralkyl halide, aralkyl alcohol or a derivative thereof described in the method for producing α-naphthol and β-naphtholphenol aralkyl.
Moreover, as a compound made to react with the phenol resin which is an alternating copolymer of the said phenolic compound and the compound which has a bivalent coupling group in presence of an acid catalyst, it is a compound represented by general formula (6-1). Can be preferably exemplified.

(In the formula, R ² represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. B represents a hydroxyl group or a halogen atom.)
Specific examples of the hydrocarbon group R ¹ in the compound represented by the general formula (6-1) include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene. , Ethylethylene, 2-methyl-tetramethylene, 2-methyl-hexamethylene, 2-ethyl-hexamethylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4 -Cyclooctylene, vinylene, propenylene, butanediylidene, 1-propanyl-3-ylidene, o-phenylene, m-phenylene, p-phenylene, 3-cyclohexene-1,2-ylene, 2,5-cyclohexadiene-1, 4-ylene and the like can be mentioned, and among these, methylene and ethylene are particularly preferable.

B is a hydroxyl group or a halogen atom, and a chlorine atom is particularly preferable among the halogen atoms.
Specific examples of the compound represented by the general formula (6-1) include 2-thiophene methanol, 3-thiophene methanol, 2-thiophene ethanol, 3-thiophene ethanol, 2-thiophene propanol, 3-thiophene propanol, 2- Thiophenebutanol, 3-thiophenbutanol, 2-thiophenpentanol, 3-thiophenpentanol, 2-thiophenhexanol, 3-thiophenhexanol, 2-thiophenheptanol, 3-thiophenheptanol, 2-thiophenoctanol, 3-thiophene Octanol, 2-thiophene cyclopropanol, 3-thiophene cyclopropanol, 2-thiophene cyclobutanol, 3-thiophene cyclobutanol, 2-thiophene cyclopentanol, 3-thiophene cyclonanol, 2-thiol Cyclohexanol, 3-cyclohexanol, 2-thiophenecycloheptanol, 3-thiophenecycloheptanol, 2-thiophenecyclooctanol, 3-thiophenecyclooctanol, 1- (2-thienyl) -2-propanol, 1- (3-thienyl) -2-propanol, 1- (2-thienyl) -2-ethyl-1-hexanol, 1- (3-thienyl) -2-ethyl-1-hexanol, alpha-cyclopropyl-2 -Thiophene methanol, alpha-cyclopropyl-3-thiophene methanol, 2-chloromethylthiophene, 3-chloromethylthiophene, 2-chloroethylthiophene, 3-chloroethylthiophene, 2-bromomethylthiophene, 3-bromomethylthiophene, 2-bromoethylthiophene, 3-bromoethylthiophene, 2-fluoromethylthiophene 3-fluoromethylthiophene, 2-fluoroethylthiophene, 3-fluoroethylthiophene, 2-iodomethylthiophene, 3-iodomethylthiophene, 2-iodoethylthiophene, 3-iodoethylthiophene, etc., and these compounds May be used alone or in combination of two or more compounds, but in particular 2-thiophene methanol, 3-thiophene methanol, 2-chloromethyl thiophene, 3-chloromethyl thiophene, 2-bromomethyl thiophene, 3-bromomethyl thiophene 2-Fluoromethylthiophene, 3-fluoromethylthiophene, 2-iodomethylthiophene, and 3-iodomethylthiophene are preferable in terms of flame retardancy.

Below, the manufacturing method of the modified phenol resin of this invention is demonstrated more concretely.
First, the phenol resin represented by the general formula (5-1) or the general formula (7-1) of the raw material and the compound represented by the general formula (6-1) in the container, an acid catalyst, and if necessary, Charge the solvent. The compound represented by the general formula (6-1) can be charged in a solution state or without being dissolved in a solvent. The reaction solution is controlled at a predetermined temperature, and the reaction is carried out for a predetermined time with stirring while distilling off water and halides produced by the reaction. After a predetermined reaction time, if a solid catalyst is used, it is removed by filtration or the like. Next, the modified phenolic resin of the present invention can be obtained by removing the solvent or the unreacted residual compound represented by the general formula (6-1) or precipitating the polymer by distillation under reduced pressure or the like.

The charging ratio of the phenol resin represented by the general formula (5-1) or the general formula (7-1) as a raw material and the compound represented by the general formula (6-1) is a hydroxyl equivalent value in the phenol resin. The compound represented by the general formula (6-1) is 10 mmol to 6 mol, preferably 50 mmol to 4 mol, and more preferably 100 mmol to 2 mol with respect to 1 mol.
Examples of the acid catalyst used in the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as acetic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and diethyl sulfuric acid, zinc chloride, aluminum chloride, Lewis acid such as iron chloride and boron trifluoride, solid acid catalyst such as zeolite, montmorillonite and activated clay, super strong acid such as trifluoromethanesulfonic acid, acidic ion exchange resin such as alkanesulfonic acid type, perfluoroalkanesulfonic acid type Examples thereof include super strong acid ion exchange resins such as p-toluenesulfonic acid and diethylsulfuric acid.

  As the usage-amount of an acid catalyst, 0.0001-10 mass in the case of liquids, such as an inorganic acid and an organic acid, with respect to the total mass of a phenol resin, the compound represented by General formula (6-1), and an acid catalyst. %, Preferably 0.001 to 5 mass%, more preferably 0.01 to 1 mass%. Moreover, in the case of solid of a solid acid catalyst and an ion exchange resin, it is 1-100 mass%, Preferably it is 10-50 mass%.

  Moreover, a solvent can be used as needed and can use any solvent in the range which does not impair the objective of this invention. Specifically, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, mesitylene, anisole, halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, hexane And hydrocarbon solvents such as heptane, octane and cyclohexane, and ester solvents such as ethyl acetate, butyl acetate and amyl acetate. The amount of the solvent used may be any amount, and considering volumetric efficiency and economic efficiency, it is preferably 20 ml or less, preferably 10 ml or less, and further preferably 5 ml or less with respect to 1 g of the raw phenol resin.

The atmosphere of the reaction system may be any of air, an inert gas such as nitrogen, argon, and helium, but a nitrogen atmosphere is particularly preferred from the viewpoint of cost performance that prevents phenol oxidation.
The reaction temperature is 40 to 250 ° C., preferably 60 to 200 ° C., more preferably 80 to 160 ° C. The reaction pressure may be any of reduced pressure, normal pressure, and pressurized, but the reaction temperature is higher than the boiling point of the solvent. In some cases, it is desirable to perform a pressure reaction using a pressure-resistant reaction vessel. Although the reaction time varies depending on the reaction temperature, etc., it is in the range of 1 to 25 hours. In reality, the disappearance of the compound represented by the general formula (6-1) is traced by high performance liquid chromatography or gas chromatography. However, it is preferable to determine the end point.

[Epoxy resin composition]
The epoxy resin composition using the modified phenolic resin of the present invention as a curing agent will be described.
The epoxy resin composition of the present invention comprises (B) a curing agent, the modified phenol resin represented by the general formula (2-1) or the general formula (3-1) of the present invention as an essential component, and (A) An epoxy resin composition comprising a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin and (C) a curing accelerator.

[(A) Bifunctional or higher functional epoxy compound or bifunctional or higher functional epoxy resin]
In the epoxy resin composition used in the present invention, (A) the bifunctional or higher functional epoxy compound or the bifunctional or higher functional epoxy resin includes all those having two or more epoxy groups in one molecule. It has an epoxy group obtained by oxidation, glycidyl etherification of a hydroxyl group, glycidyl amination of a primary or secondary amine, glycidyl esterification of a carboxylic acid, or the like.

 Specifically, dihydroxybenzenes such as catechol, resorcin, hydroquinone; 2,6-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2- (3-hydroxyphenyl)- 2- (4′-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane (bisphenol F), bis (4-hydroxyphenyl) sulfone (bisphenol S), bis (4-hydroxyphenyl) sulfide, bis (4- Hydroxyphenyl) methylcyclohexane, bis (4-hydroxyphenyl) methylbenzene, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxy-2,2′6,6′-tetramethylbiphenyl, 4,4′-dihydroxy Diphenyl ether, 6,6'-dihydroxy-3,3,3 ', 3'-tetra Bisphenols such as methyl-1,1-spiroindane, 1,3,3-trimethyl-1- (4-hydroxyphenyl) -1-indan-6-ol; tetraphenylolethane, naphthol-cresol resol condensate Oligophenols such as: phenol novolaks, residues obtained by removing bisphenol compounds from novolacs [triphenols or higher: hereinafter referred to as VR]; phenol-dicyclopentadiene resins, phenol aralkyl resins, biphenyl aralkyl resins Phenol resins such as naphthol aralkyl resins; ethylenediamine, propylenediamine, hexamethylenediamine, aniline, 4,4′-diaminodiphenylmethane (MDA), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 2,2-bis (4,4'- Diaminophenyl) propane, m-xylylenediamine, p-xylylenediamine, 1,2-diaminocyclohexane, aniline aralkyl resin represented by general formula (8-1) [trade name: Anilix, Mitsui Chemicals, Inc. Aliphatic or aromatic amines such as

(In the formula, R ¹ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms. The number of repeating units n represents an integer of 0 to 50, and the average is in the range of 0 to 15). M-aminophenol, p-aminophenol, 2- (4-aminophenyl) -2- (4′-hydroxyphenyl) propane, 4-aminophenyl- (4′-hydroxyphenyl) methane, etc. Aminophenols of phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, and hydroxycarboxylic acids such as 1,3 benzoic acid.

Glycidylation of these compounds having active hydrogen can be carried out by a known method, and epichlorohydrin is most commonly reacted in the presence of a hydrogen halide acceptor. In producing glycidyl esters, it is also known that a method of reacting a carboxylic acid methyl ester with glycidol using a metal catalyst, particularly a thallium compound such as TlNO ₃ or Tl (OCOCF ₃ ) ₃ as a catalyst, is also known. .

These bifunctional or higher functional epoxy compounds or bifunctional or higher functional epoxy resins may be used alone or in combination of two or more.
[(B) Curing agent]
The epoxy resin composition used in the present invention is characterized by using the modified phenolic resin of the present invention as an essential component as the (B) curing agent, and may be used alone or in combination of two or more. (B) The modified phenolic resin used as the curing agent is blended so that the hydroxyl equivalent of the (B) curing agent is in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy equivalent of the epoxy resin. It is preferable that it is blended so as to be in the range of 0.75 to 1.1 equivalents.

In the present invention, when the modified phenolic resin used as the curing agent (B) is blended in the above range, a cured product excellent in both flame retardancy and adhesion is obtained.
[(C) Curing accelerator]
The (C) curing accelerator used in the present invention is not particularly limited as long as it accelerates the curing reaction between the epoxy resin and the phenol compound or the resin. Curing accelerators used at this time are tributylphosphine, triphenylphosphine, tris (dimethoxyphenylphosphine), tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine, tris (trimethoxyphenyl) phosphine, tris (dimethoxyphenyl) phosphine Phosphines such as tris (trimethylphenyl) phosphine and tris (dimethylphenyl) phosphine; Phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate; 2-methylimidazole, 2 -Phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyano Ethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine, 2,4-dicyano-6- [2-undecylimidazolyl- (1) Imidazoles such as] -ethyl-S-triazine, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetraphenylborate, 2-ethyl Imidazolium salts such as -1,4-dimethylimidazolium tetraphenylborate; pyridines such as N-dimethylaminopyridine, 2,4,6-tris (dimethylaminomethyl) phenol, benzylmethylamine, tetramethylbutylguanidine, Amines such as N-methylpiperazine, 2-dimethylamino-1-pyrroline; triethylammonium tetra Ammonium salts such as phenylborate, 1,5-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene, 1,4-diazabicyclo (2,2 , 2) -octane and other diazabicyclo compounds; these diazabicyclo compounds tetraphenylborate salts, phenol salts, phenol novolac salts, 2-ethylhexane salts and the like.

These (C) curing accelerators may be used singly or in combination of two or more, and the amount used is (A) a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin and (B) curing. It is 0.1-7 mass% with respect to the total mass of an agent, More preferably, it is 0.5-3 mass%.
[(D) Organic and / or inorganic filler]
In the epoxy resin composition of the present invention, (D) organic and / or inorganic fillers and other additives can be used as necessary. In particular, when used as a sealing material for semiconductor integrated circuits, organic and / or inorganic fillers are used to improve the mechanical properties and reduce the overall cost, and colorants such as carbon black are used to prevent malfunction due to light. Furthermore, it is desirable to use a mold release agent, a coupling agent, a flame retardant, a plasticizer, a reactive diluent, a pigment and the like.

As usage-amount of an organic and / or inorganic filler, it is 100-1900 mass parts range with respect to 100 mass parts of total mass of (A) bifunctional or more epoxy compound or bifunctional or more epoxy resin, and (B) hardening | curing agent. Preferably, it is 250-1900 mass parts, More preferably, it is 550-1900 mass parts or more.
Organic and / or inorganic fillers used include silica, alumina, silicon nitride, silicon carbide, talc, calcium silicate, calcium carbonate, mica, clay, titanium white powder, glass fiber, carbon fiber, aramid fiber, etc. And the like. Of these, crystalline silica and / or fused silica are preferable for use as a sealing material, and the shape of the resin composition is spherical or spherical or a mixture of spherical and crushed in consideration of fluidity during molding of the resin composition. desirable.

  Furthermore, it is preferable to add various additives in consideration of mechanical strength and heat resistance. For example, it is desirable to use a coupling agent to improve the adhesion between the resin and the inorganic filler, and examples of such a coupling agent include silane-based, titanate-based, aluminate-based, or zircoaluminate-based. be able to. Of these, a silane coupling agent is preferable, and a silane coupling agent having a functional group that reacts with an epoxy group is particularly preferable.

  Such coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples thereof include ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These can be used alone or in combination of two or more. These coupling agents are desirably immobilized on the surface of the inorganic filler in advance by adsorption or reaction.

[Hardened epoxy resin]
The cured epoxy resin of the present invention is a cured product obtained by thermally curing the epoxy resin composition of the present invention. The curing temperature is 100 ° C. to 220 ° C., more preferably 150 ° C. to 200 ° C., and the curing time is 1 minute to 20 hours, more preferably 1 hour to 10 hours.
Moreover, the epoxy resin hardened | cured material of this invention excellent in adhesiveness and a flame retardance can be obtained by thermosetting the said epoxy resin composition of this invention.

[Semiconductor device]
The semiconductor device of the present invention is obtained by sealing a semiconductor integrated circuit using the epoxy resin composition of the present invention. As a method for manufacturing a semiconductor device, low-pressure transfer molding is the most common, but other methods such as injection molding, compression molding, and cast molding are also possible. A special technique using a solvent is also possible.

Next, the prepreg according to the present invention, a laminated board formed by laminating the prepreg, and an electronic circuit board using the laminated board will be specifically described.

The epoxy resin composition used for the prepreg of the present invention contains the following (A) a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin, (B) a curing agent, and (C) a curing accelerator. ing.
[(A) Bifunctional or higher functional epoxy compound or bifunctional or higher functional epoxy resin]
(A) The bifunctional or higher functional epoxy compound or bifunctional or higher functional epoxy resin used in the present invention includes all those having two or more epoxy groups in one molecule, such as oxidation of olefins and hydroxyl group glycidyl ether. , Glycidyl amination of primary and secondary amines, glycidyl esterification of carboxylic acid, and the like.
i) Raw material of epoxy compound or epoxy resin Specific examples of hydroxyl groups used for glycidyl etherification of hydroxyl groups include dihydroxybenzenes such as catechol, resorcin, and hydroquinone; 2,6-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2- (3-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane (bisphenol F), bis (4-hydroxy Phenyl) sulfone (bisphenol S), bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) methylcyclohexane, bis (4-hydroxyphenyl) methylbenzene, 4,4′-dihydroxybiphenyl, 4,4′- Dihydroxy-2,2 '6,6'-te Lamethylbiphenyl, 4,4′-dihydroxydiphenyl ether, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1-spiroindane, 1,3,3-trimethyl-1- (4 -Hydroxyphenyl) -1-indan-6-ol and other bisphenols; tetraphenolol ethane, oligophenols such as naphthol-cresol resol condensates; phenol novolacs, residues obtained by removing bisphenol compounds from novolacs Phenol resins such as phenol-dicyclopentadiene resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, and the like. In particular, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-2,2'6,6'-tetramethylbiphenyl bisphenols; phenol novolacs, phenol dicyclopentadiene resins, phenol aralkyl resins, biphenyl aralkyl Phenol resins such as resins and naphthol aralkyl resins are preferred.

  Specific examples having an amino group used for glycidyl amination of primary and secondary amines include ethylenediamine, propylenediamine, hexamethylenediamine, aniline, 4,4′-diaminodiphenylmethane (MDA), 4,4′- Diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 2,2-bis (4,4′-diaminophenyl) propane, m-xylylenediamine, p-xylylenediamine, 1,2-diaminocyclohexane, the above general formula Aliphatic amines and aromatic amines such as aniline aralkyl resin represented by (8-1) [trade name: Anilix, manufactured by Mitsui Chemicals, Inc.], and m-aminophenol, p-aminophenol, 2 -(4-Aminophenyl) -2- (4'-hydroxyphenyl) propane, 4-aminophenyl- (4'-hydroxy) Eniru) like amino phenols such as methane. In particular, the aniline aralkyl resin represented by the general formula (8-1) is preferable, and a compound, a polymer, or a mixture thereof having 0 to 15 repeating units is most preferable.

Specific examples of the carboxyl group used for glycidyl esterification of carboxylic acid include hydroxycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, and 1,3 benzoic acid. Etc. that are epoxies.
ii) Production method of epoxy compound or epoxy resin Glycidylation of the above-mentioned compounds having active hydrogen such as hydroxyl group, amino group, and carboxyl group can be carried out by a known method, and epichlorohydrin is reacted in the presence of a hydrogen halide acceptor. It is the most common. In producing glycidyl esters, it is also known that a method of reacting a carboxylic acid methyl ester with glycidol using a metal catalyst, particularly a thallium compound such as TlNO ₃ or Tl (OCOCF ₃ ) ₃ as a catalyst is also known.

The bifunctional or higher functional epoxy compound or bifunctional or higher epoxy resin obtained from the above compound may be used alone, in combination of two or more, or in combination of an epoxy compound and an epoxy resin, and any combination thereof. You may use in the ratio.
[(B) Curing agent]
The (B) curing agent used in the present invention is a phenol resin which is an alternating copolymer of at least one phenol compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group, and Examples of the side chain of the aromatic ring having a hydroxyl group in which the resin is present include the modified phenol resin into which the group represented by the general formula (1-1) is introduced.

More preferably, it is a phenol resin which is an alternating copolymer of at least one phenol compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group, and an aromatic having a hydroxyl group in which the resin exists. It is a modified phenolic resin in which a group represented by the following general formula (1-2) is introduced as a ring side chain.

(In the formula, R ¹ represents an alkylene group having 1 to 3 carbon atoms, a 1,4-cyclohexylene group, or a phenylene group.)
Hereinafter, the modified phenol resin substituted and introduced with the group represented by the general formula (1-2) will be specifically described as the (B) curing agent.
i) Phenol resin raw material (before modification)]
Specific examples of the phenol compound used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, pn-propylphenol, and p-isopropylphenol. 2,4-xylenol, 2,6-xylenol, 4,6-xylenol, 3,5-xylenol, 2,4,6-trimethylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o -Chlorophenol, m-chlorophenol, p-chlorophenol, o-fluorophenol, m-fluorophenol, p-fluorophenol, o-dihydroxybenzene, m-dihydroxybenzene, p-dihydroxybenzene, o-methoxyphenol, m -Methoxyphenol, p-methoxypheno o- ethoxy phenol, m- ethoxy phenol, p- ethoxy phenol, p- propoxy phenol, alpha-naphthol, such as β- naphthol. They may be used alone or in combination of two or more. Among them, preferred are phenol, o-cresol, m-cresol, p-cresol, α-naphthol and β-naphthol, and particularly preferred are phenol and α-naphthol.
ii) Raw material of linking group A The linking group A is a methylene group, ethylene group, propylene group, isopropylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene group, 1,4-cyclooctylene group. O-phenylene group, m-phenylene group, p-phenylene group, 1,2-xylylene group, 1,3-xylylene group, 1,4-xylylene group, 1,2-xylylene-biphenyl group, 1,3- Xylylene-biphenyl group, 1,4-xylylene-biphenyl group, the above general formula (4-1) and the like can be mentioned. In particular, methylene group, 1,2-xylylene group, 1,3-xylylene group, 1,4-xylylene group, 1,2-xylylene-biphenyl group, 1,3-xylylene-biphenyl group, 1,4-xylylene- A biphenyl group and the general formula (4-1) are preferable. In particular, a methylene group, an ethylene group, an m-phenylene group, a p-phenylene group, a 1,3-xylylene-biphenyl group, a 1,4-xylylene-biphenyl group, and the above general formula (4-1) are preferable. With these linking groups A, good adhesion and flame retardancy, which are the effects of the present invention, can be obtained.

  Specific examples of the raw material compound to be the linking group A include 1) formaldehyde for the phenol novolac resin, 2) dicyclopentadiene for the phenol-dicyclopentadiene resin, and 3) for the phenol aralkyl resin. , Aralkyl compounds α, α′-dichloro-p-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α, α′-dibromo-p-xylene, α Α, α′-dihaloxylenes such as α, α′-dibromo-m-xylene, α, α′-dibromo-o-xylene; α, α′-dihydroxy-p-xylene, α, α′-dihydroxy- x-ylene glycols of m-xylene, α, α'-dihydroxy-o-xylene; α, α'-dimethoxy-p-xylene, α, α'-dimethoxy-m-xylene, α, α'-dimethoxy-o -Xylene, α, α'-diethoxy-p-xylene, α, α'- Ethoxy-m-xylene, α, α'-diethoxy-o-xylene, α, α'-dipropoxy-p-xylene, α, α'-dipropoxy-m-xylene, α, α'-dipropoxy-o-xylene, α, α'-diisopropoxy-p-xylene, α, α'-diisopropoxy-m-xylene, α, α'-diisopropoxy-o-xylene, α, α'-di-tert-butoxy- p-xylene, α, α'-di-tert-butoxy-m-xylene, α, α'-di-tert-butoxy-m-xylene, α, α'-di-n-butoxy-p-xylene, α Α, α'-dialkoxyxylenes such as α, α'-di-n-butoxy-m-xylene, α, α'-di-n-butoxy-o-xylene, etc. 4) Phenol biphenyl aralkyl resin Is a biphenylaralkyl halide or a biphenylaralkyl compound thereof, 2,2′-bischloromethylbiphenyl 2,3'-bischloromethylbiphenyl, 2,4'-bischloromethylbiphenyl, 3,3'-bischloromethylbiphenyl, 3,4'-bischloromethylbiphenyl, 4,4'-bischloromethyl Biphenyl, 2,2'-bisbromomethylbiphenyl, 2,3'-bisbromomethylbiphenyl, 2,4'-bisbromomethylbiphenyl, 3,3'-bisbromomethylbiphenyl, 3,4'-bisbromomethyl Examples thereof include dihalogenomethylbiphenyls such as biphenyl and 4,4′-bisbromomethylbiphenyl. 5) As the naphthol aralkyl resin, all of the raw materials described in 1) to 5) above can be used.

  Preferably, 1) formaldehyde for phenol novolac resins, 2) dicyclopentadiene for phenol-dicyclopentadiene resins, 3) α, α'-dichloro-p-xylene, α, α for phenol aralkyl resins. '-Dichloro-m-xylene, 4) For phenol biphenyl aralkyl resin, 3,3'-bischloromethyl biphenyl, 4,4'-bischloromethyl biphenyl, 5) For naphthol aralkyl resin, formaldehyde, dicyclopentadiene , Α, α′-dichloro-p-xylene, 3,3′-bischloromethylbiphenyl, 4,4′-bischloromethylbiphenyl.

Any of these raw materials may be used alone or in combination of two or more aralkyl compounds.
iii) Method for Producing Phenol Resin An alternating copolymer, that is, a phenol resin is obtained by a condensation reaction using the above-described phenol compound and the above-described raw material that becomes the divalent linking group A. The production method is not particularly limited, and all known methods can be applied. Specifically, a phenol, a linking group, and an acid catalyst are charged and reacted for several hours while maintaining the reaction temperature at 80 to 150 ° C. to obtain a crude phenol resin. Furthermore, the phenol resin refine | purified by dephenol-izing under 150 degreeC or more under reduced pressure is obtained.
iv) Side chain raw material of modified phenol resin Specific examples of R ¹ which is a divalent group of the above general formula (1-2) are methylene group, ethylene group, propylene group, isopropylene group, 1,4-cyclohexene. A silene group and a phenylene group, preferably a methylene group and an ethylene group.

  Specific examples of the raw material compound represented by the general formula (1-2) used for introducing the general formula (1-2) which is a side chain and a monovalent group are 2-thiophene methanol, 3-thiophene methanol, 2-thiophene ethanol, 3-thiophene ethanol, 2-thiophene propanol, 3-thiophene propanol, 2-thiophene cyclohexanol, 3-cyclohexanol, 2-thiophene cyclooctanol, 3-thiophene cyclooctanol, 1- (2 -Thienyl) -2-propanol, 1- (3-thienyl) -2-propanol, 2-chloromethylthiophene, 3-chloromethylthiophene, 2-chloroethylthiophene, 3-chloroethylthiophene, 2-bromomethylthiophene, 3-bromomethylthiophene, 2-bromoethylthiophene, 3-bromoethylthiophene, 2- Fluoromethylthiophene, 3-fluoromethylthiophene, 2-fluoroethylthiophene, 3-fluoroethylthiophene, 2-iodomethylthiophene, 3-iodomethylthiophene, 2-iodoethylthiophene, 3-iodoethylthiophene-2-thiophenephenol, 3-thiophenephenol, 2-thiophene chlorobenzene, 3-thiophene chlorobenzene, 2-thiophene bromobenzene, 3-thiophene bromobenzene, and the like.

These compounds may be used alone or in combination of two or more. Especially 2-thiophene methanol, 3-thiophene methanol, 2-chloromethyl thiophene, 3-chloromethyl thiophene, 2-bromomethyl thiophene, 3-bromomethyl thiophene, 2-fluoromethyl thiophene, 3-fluoromethyl thiophene, 2-iodo Methylthiophene and 3-iodomethylthiophene are preferable in terms of flame retardancy.
v) Modification Method of Phenol Resin A phenol resin is reacted with a raw material compound represented by the general formula (1-2), particularly the general formula (6-1), so that the side chain of the phenol resin is represented by the general formula (1-2). The method for introducing a monovalent group represented by the above, that is, the method for modifying the phenol resin is not particularly limited, and all known methods can be applied.

  Specifically, the phenol resin and the raw material compound represented by the general formula (1-2) are used in a solution state or in a suspended state (heterogeneous system) in the presence of an acid catalyst, using a solvent as necessary. The reaction is carried out while distilling off the water and halide produced in the reaction. The atmosphere of the reaction system is preferably in air or an inert gas such as nitrogen, argon, or helium. The reaction temperature is 40 to 250 ° C., preferably 60 to 200 ° C., more preferably 80 to 160 ° C., and the reaction time is actually determined by high-performance liquid chromatography or gas chromatography while determining the end point. Is generally in the range of 1 to 25 hours.

The raw material compound which becomes general formula (1-2) and a preparation ratio with a phenol resin and the raw material compound which becomes general formula (1-2) with respect to 1 mol of hydroxyl equivalent values in this phenol resin are 10 mmol-6 mol. , Preferably 50 mmol to 4 mol, more preferably 100 mmol to 2 mol.
Examples of acid catalysts used include inorganic acids such as acid, sulfuric acid and phosphoric acid, organic acids such as acetic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid and diethylsulfuric acid, zinc chloride, aluminum chloride, iron chloride, Lewis acid such as boron fluoride, solid acid catalyst such as zeolite, montmorillonite, activated clay, super strong acid such as trifluoromethane sulfonic acid, acidic ion exchange resin such as alkane sulfonic acid type, super strong acid such as perfluoroalkane sulfonic acid type An ion exchange resin etc. are mentioned, It may use individually or in combination of 2 or more types, and p-toluenesulfonic acid and diethyl sulfuric acid are preferable.

The amount of the acid catalyst used is 0.0001 to 10% by mass in the case of a liquid such as an inorganic acid or an organic acid with respect to the total mass of the phenol resin, the compound represented by the general formula (6-1) and the acid catalyst. , Preferably it is 0.001-5 mass%, More preferably, it is 0.01-1 mass%. Moreover, in the case of solid of a solid acid catalyst and an ion exchange resin, it is 1-100 mass%, Preferably it is 10-50 mass%.
vi) Properties of Modified Phenolic Resin The modified phenolic resin has the heat resistance, flame retardancy and adhesion of the present invention by introducing a monovalent group represented by the general formula (1-2) as a side chain of the phenolic resin. Excellent performance is obtained. Further, mechanical properties such as bending strength and flexural modulus and resin hygroscopicity have equivalent performance without impairing the performance of the phenol resin before modification.

  When the sulfur atom is 0.01 mol or less with respect to 1 mol of the hydroxyl group of the modified phenolic resin, the heat resistance, flame retardancy and adhesion properties of the present invention cannot be obtained. Moreover, when the sulfur atom is 2 mol or more with respect to 1 mol of the hydroxyl group of the modified phenolic resin, the curing rate is remarkably slowed. Alternatively, there is a problem that the modification of the phenol resin takes time and productivity is lowered.

The hydroxyl group content in the modified phenolic resin of the present invention is determined, for example, by acetylating with acetic anhydride using pyridine as a solvent and titrating the acetic acid produced after decomposing the excess reagent with water with a potassium hydroxide solution. be able to. The sulfur atom content can be determined by a method such as NMR analysis using a chloroform solvent. In order to obtain sufficient heat resistance, flame retardancy and adhesion performance, the hydroxyl equivalent of the modified phenolic resin is 101 to 440 g / eq, preferably 105 to 400 g / eq, more preferably 110 to 350 g / eq.
vii) Specific Examples of Modified Phenol Resin The modified phenol resin is preferably the above general formula (2-2) or general formula (3-2). In general formula (2-2) or general formula (3-2), as R ² which is a monovalent substituent, specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxy group, Examples thereof include an ethoxy group, a propoxy group, an isopropoxy group, a phenyl group, a fluorine atom, a chlorine atom, and a hydroxyl group, and among these, a hydrogen atom, a hydroxyl group, a methyl group, and a methoxy group are particularly preferable. These monovalent substituents R ² are determined by the structure of the phenol compound that is the raw material of the phenol resin.

  In the general formula (2-2), x and z are integers of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and y is an integer of 0 to 3, preferably 0. It is preferable that it is an integer of ˜2, more preferably an integer of 0-1. The total number of x, y and z is preferably an integer of 1 to 11, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. The number of repeating units n is preferably an integer of 0 to 50, more preferably an integer of 0 to 15. Particularly preferably, it is an integer of 2 to 10.

  In the general formula (3-2), x and z are integers of 0 to 6, preferably 0 to 3, more preferably 0 to 1, and y is an integer of 0 to 5, preferably 0. It is preferable that it is an integer of ˜2, more preferably an integer of 0-1. The total number of x, y and z is preferably an integer of 1 to 17, preferably an integer of 1 to 10, and more preferably an integer of 1 to 3. The number of repeating units n is preferably an integer of 0-50, more preferably an integer of 0-15. Most preferably, n has a certain range and is a compound, a polymer, or a mixture thereof.

  In general formula (2-2) or general formula (3-2), the number of repeating units n is preferably an integer of 0 to 50, more preferably 0 to 15. Further, the repeating unit number n is preferably an integer of 0 to 15, more preferably an integer of 0 to 15. Particularly preferably, it is an integer of 2 to 10. Most preferably, n has a certain range and is a compound, a polymer, or a mixture thereof.

When the above general formula (2-2) or general formula (3-2) is shown more specifically, 20 modified phenolic resins represented by the general formulas (1) to (20) are particularly preferable.
viii) Use amount of curing agent of (B) The use amount of curing agent of (B) which is a modified phenolic resin is based on (A) 100 parts by weight of bifunctional or higher functional epoxy compound or bifunctional or higher functional epoxy resin. The range of 2 to 150 parts by weight is preferable, more preferably 20 to 140 parts by weight, particularly preferably 40 to 130 parts by weight, and most preferably 70 to 120 parts by weight. (B) When the amount of the curing agent used is less than 2 parts by weight, (A) the flame retardancy decreases due to an increase in the bifunctional or higher functional epoxy compound or the bifunctional or higher functional epoxy resin, or the effect of the present invention. Some adhesion cannot be obtained. On the other hand, when the amount used exceeds 150 parts by weight, problems such as a decrease in Tg of the cured product and a decrease in mechanical strength occur.
[(C) Curing accelerator]
The (C) curing accelerator used in the present invention is not particularly limited as long as it accelerates the curing reaction between the epoxy resin and the phenolic compound or the resin. Specific examples of the curing accelerator include tributylphosphine, Triphenylphosphine, tris (dimethoxyphenylphosphine), tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine, tris (trimethoxyphenyl) phosphine, tris (dimethoxyphenyl) phosphinetris (trimethylphenyl) phosphine, tris (dimethylphenyl) Phosphines such as phosphine; tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate, etc. Phosphonium salts; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl -(1)]-Ethyl-S-triazine, 2,4-dicyano-6- [2-undecylimidazolyl- (1)]-imidazoles such as ethyl-S-triazine, 1-cyanoethyl-2-undecyl Imidazolium salts such as imidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetraphenylborate, 2-ethyl-1,4-dimethylimidazolium tetraphenylborate; N-dimethyl Pyridines such as aminopyridine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyl ester Amines such as ruamine, tetramethylbutylguanidine, N-methylpiperazine, 2-dimethylamino-1-pyrroline; ammonium salts such as triethylammonium tetraphenylborate, 1,5-diazabicyclo (5,4,0) -7- Diazabicyclo compounds such as undecene, 1,5-diazabicyclo (4,3,0) -5-nonene, 1,4-diazabicyclo (2,2,2) -octane; these diazabicyclo compounds tetraphenylborate salts, phenol salts, Phenol novolac salts, 2-ethylhexane salts and the like can be mentioned.

You may use these (C) hardening accelerators individually or in mixture of 2 or more types. The amount used is 0.1 to 7% by weight, more preferably 0.3 to 7% by weight based on the total weight of (A) a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin and (B) a curing agent. 5% by weight. Especially preferably, it is 0.5 to 3 weight%, and 0.8 to 2 weight is the most preferable.
(C) When the use amount of the curing accelerator is less than 0.1% by weight, the curing rate becomes slow, sufficient curing cannot be performed, and excellent properties of the epoxy resin composition cannot be obtained, or curing It takes a long time to produce a problem such as a significant decrease in productivity. On the other hand, if the amount used exceeds 7% by weight, the curing rate is too fast, so that the curing itself becomes uncontrollable, or when using a curing accelerator having a polar group, the moisture absorption rate is increased. Problems such as reduced heat resistance occur.
[Epoxy resin composition]
The epoxy resin composition of the present invention contains (A) a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin, (B) a curing agent, and (C) a curing accelerator.
i) Manufacturing method There is no restriction | limiting in particular in the manufacturing method of an epoxy resin composition, All the well-known methods are applicable. Specifically, (A) a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin, (B) a curing agent, and (C) a curing accelerator are applied for several minutes to several hours in a pulverizer such as a Henshur mixer. , Dry blend and mix. The mixed powder is weighed together with a solvent in a separable flask or the like and dissolved at room temperature using a stirrer or the like to prepare a varnish of an epoxy resin composition. The varnish of the epoxy resin composition is recrystallized as the storage time becomes longer. Alternatively, it is better to avoid long-term storage in varnish because problems such as changes in physical properties occur.
ii) Epoxy Equivalent of Epoxy Resin Composition In the present invention, the epoxy equivalent is preferably a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin in the range of 170 to 1000 g / eq. More preferably, the epoxy equivalent is in the range of 180 to 600 g / eq, more preferably 200 to 400 g / eq. When the epoxy equivalent is lower than 170, the water absorption rate of the cured product increases and the moisture absorption heat resistance decreases. On the other hand, if it is higher than 1000 g / eq, the impregnation and solubility are deteriorated, and the Tg of the cured product is lowered to affect the heat resistance.
iii) Compounding amount (B) The curing agent is blended in such a way that (A) the epoxy equivalent of the bifunctional or higher functional epoxy compound or the bifunctional or higher epoxy resin is equivalent to 1 equivalent, the hydroxyl equivalent of the (B) curing agent is 0.3 It is preferable to mix | blend so that it may become in the range of -1.5 equivalent, Furthermore, it is preferable to mix | blend so that it may become the range of 0.6-1.2 equivalent. When blending in the above range, a cured product excellent in both flame retardancy and adhesion is obtained, which is preferable.

(A) Use amount of (B) curing agent to bifunctional or higher epoxy compound or bifunctional or higher epoxy resin, and (A) Bifunctional or higher functional epoxy compound or bifunctional or higher epoxy resin and (B) curing agent The amount of (C) curing accelerator used relative to the total weight of is as described above.
iv) Filler The epoxy resin composition may contain a filler as necessary. Examples of the filler include an organic filler and an inorganic filler. Specific examples of the organic filler include powder epoxy resin (for example, TEPIC), melamine. Resin, benzoguanamine resin, urea resin, cross-linked acrylic polymer, and the like. Specific examples of the inorganic filler include magnesium oxide, calcium carbonate, zirconium silicate, zirconium oxide, calcium silicate, aluminum hydroxide, magnesium hydroxide, water. Examples include calcium oxide, titanium oxide, silicon carbide, alumina, boron nitride, silica, glass cloth, glass fiber, and alumina fiber. Among these, calcium carbonate is particularly preferable from the viewpoint that surface roughening when used as an insulating layer becomes easy and adhesion strength with a conductor can be increased.
[Prepregs, laminates, and electronic circuit boards]
The prepreg, laminated board, and electronic circuit board of the present invention are obtained by forming a layer comprising an epoxy resin composition and a glass substrate on at least one surface of a metal layer on which a copper foil or a wiring layer is formed. is there.

  Any of the methods for producing the prepreg, the laminate, and the electronic circuit board of the present invention. It can be carried out according to a known method and is not particularly limited. Specifically, the epoxy resin composition of the present invention is dissolved in a solvent to prepare a varnish having a resin content of 30 to 70 wt%, varnished, and impregnated into a glass substrate such as a glass woven fabric or a glass nonwoven fabric, Dry at 120 to 180 ° C. and 80 to 250 ° C. to obtain a prepreg. When impregnation or drying is performed under reduced pressure for the purpose of defoaming or increasing the drying speed. A woven fabric or non-woven fabric other than glass may be used, or may be used in combination with the glass woven fabric or non-woven fabric. A necessary number of the prepregs thus obtained are stacked and heated and pressed to obtain a laminate. Furthermore, an electronic circuit board is obtained by combining a laminated board and copper foil, and heating and pressurizing.

  In the heating / pressurizing step, the epoxy resin composition is heat-treated, and the method is not particularly limited, and any known method can be applied. Specifically, using a general-purpose pressure press or the like, the temperature is 150 to 250 ° C., the heating time is 1 minute to 10 hours, the pressure is 0 to 3 MPa. In order to prevent coloring, it can be carried out in an inert gas atmosphere such as nitrogen, helium or argon, in an air stream, or under reduced pressure.

The glass substrate such as glass woven fabric and glass nonwoven fabric used in the above production method is not particularly limited, and commercially available products that are always available can be used.
In addition to the above production method, in the step of obtaining the above laminated board, a method of obtaining an electronic circuit board at a time by simultaneously superimposing copper foils, a varnish or paste of an epoxy resin composition, a metal foil such as copper The method of apply | coating to, the method of bonding with metal foils, such as copper, after processing an epoxy resin composition in the form of a sheet | seat or a film, etc. are applicable.

In the case of making a varnish or paste, there is no restriction in a dissolved state or a non-uniform suspension state. Specific examples of the solvent that can be used include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and aromatics such as toluene and xylene. There are aromatic hydrocarbons, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, and butyl cellosolve acetate. Can be mixed and used.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these. In addition, the physical property value of the polymer obtained in the Example was measured with the following method.
[Geltime]
When the epoxy resin composition was cured while stirring on a hot plate at a temperature of 175 ° C., the gel time was determined by measuring the time from the start of heating until the epoxy composition was cured and visually disappearing of the twisting property.
[Glass transition temperature; Tg]
The epoxy resin composition was weighed in an aluminum cup and after-curing was performed at 175 ° C. for 8 hours in a nitrogen atmosphere in an inert oven, and then measured by a needle approach method using a TMA device (Shimadzu TMA-50). (Needle diameter 0.5 mm, load 10 g, constant speed load mode, measurement conditions are 5 ° C./min, room temperature to 300 ° C., atmosphere nitrogen gas, flow rate 100 ml / min).
[Bending elastic modulus]
Epoxy resin composition 14.5 parts by mass (catalyst 2 parts by mass is counted as an external number, so the total number is 102 parts by mass), waxes 0.5 parts by mass (carnauba and Hoechst E), spherical silica 87 parts by mass (YXK -35R, manufactured by Tatsumori Co., Ltd.), and B stage was performed by overheating kneading with a roll at 100 ° C. for 3 minutes. The obtained compound was filled in a mold and held at 175 ° C. for 200 seconds. After transfer molding, post-curing was performed at 175 ° C. for 8 hours in an inert oven in a nitrogen atmosphere. The bending elastic modulus was measured based on JIS K-6911 using the obtained test piece.
[Bending strength]
Epoxy resin composition 14.5 parts by mass (catalyst 2 parts by mass is counted as an external number, so the total number is 102 parts by mass), waxes 0.5 parts by mass (carnauba and Hoechst E), spherical silica 87 parts by mass (YXK -35R, manufactured by Tatsumori Co., Ltd.), and B stage was performed by overheating kneading with a roll at 100 ° C. for 3 minutes. The obtained compound was filled in a mold and held at 175 ° C. for 200 seconds. After transfer molding, post-curing was performed at 175 ° C. for 8 hours in an inert oven in a nitrogen atmosphere. The bending strength was measured based on JIS K-6911 using the obtained test piece.
[Hygroscopic rate]
The moisture absorption rate was calculated based on the following equation by measuring the mass before and after absorbing moisture in an atmosphere of temperature 85 ° C. and humidity 85% for 168 hours.

Moisture absorption [mass%] = (W2-W1) / W1
W1: Sample mass before standing in an atmosphere of temperature 85 ° C. and humidity 85% W2: Sample mass after standing in an atmosphere of temperature 85 ° C. and humidity 85% after 168 hours [flame retardancy]
Measurement of bending elastic modulus The compound obtained at the time of preparing the test piece was filled in a mold and held at 150 ° C. for 10 minutes for press molding. Next, after post-curing in an inert oven at 175 ° C. for 8 hours in a nitrogen atmosphere, the obtained test piece was cut out and subjected to V determination based on a flame-retardant test piece vertical according to the combustion test method UL94. .
[Reflow resistance]
The compound obtained at the time of preparing the test piece for measuring the flexural modulus was filled into a mold, held at 175 ° C. for 200 seconds, and a package of 20 mm long × 20 mm wide × 1.75 mm thick was manufactured with a transfer molding machine. Next, after being post-cured in an inert oven at 175 ° C. for 8 hours in a nitrogen atmosphere, it was allowed to absorb moisture by leaving it in an atmosphere of 85 ° C. and 85% humidity. When time passed, 96 hours passed, and 168 passed, 5 packages were removed from the moisture absorption atmosphere each time, put into a reflow furnace, and kept at 250 ° C. for 10 seconds. Next, the package was taken out and cooled to room temperature, and the adhesion state of the resin and the frame was observed with an ultrasonic microscope for five packages to confirm the presence or absence of cracking and peeling. Next, the durable moisture resistance time was calculated based on the following formula.

Durability and moisture resistance time (hours) = 24 × (S1 / 5) + 48 × (S2 / 5) + 72 × (S3 / 5) + 96 × (S4 / 5) + 168 × (S5 / 5)
S1: Number of packages not cracked or peeled after 24 hours of moisture absorption
S2: Number of packages that did not crack or peel after 48 hours of moisture absorption
S3: Number of packages that did not crack or peel due to moisture absorption for 72 hours
S4: Number of packages that did not crack or peel after 96 hours of moisture absorption
S5: Number of packages that did not crack or peel due to moisture absorption for 168 hours [content of hydroxyl group in phenol resin]
The hydroxyl group content in the phenol resin was determined by acetylating with acetic anhydride using pyridine as a solvent, and titrating the acetic acid produced after decomposing the excess reagent with water with a potassium hydroxide solution.
[Sulfur atom content in phenolic resin]
The content of sulfur atoms in the phenol resin was determined by a method based on elemental analysis such as NMR analysis and IR analysis in a chloroform solvent.

[Synthesis Example 1]
Phenol novolac resin (trade name: PSM4261, manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl group equivalent 107 g / eq) 53.5 g (0.5 mol = hydroxyl group), 2-thiophenmethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 28 0.5 g (0.25 mol = sulfur atom) was weighed, thermometer, dropping funnel, Dean-Stark moisture separator, reflux condenser, nitrogen inlet tube and a glass reaction vessel equipped with a stirring device, and under nitrogen flow The temperature was raised to 140 ° C. After confirming that it was uniformly melted while keeping the internal temperature at 140 ° C., 0.2 g of diethyl sulfuric acid was injected with a syringe. After completion of the injection, the reaction was carried out for 4 hours while separating and removing water generated at the same temperature. After confirming that 2-thiophene methanol does not exist in the system by gel permeation chromatography (model 830RI, manufactured by JASCO Corporation) and gas chromatography (model GC-1700, manufactured by Shimadzu Corporation), it is represented by chemical formula (1). The modified phenolic resin was discharged into a SUS vat.

[Synthesis Example 2]
A phenol novolak resin (trade name: PSM4261, manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl group equivalent 107 g / eq) 53.5 g (0.5 mol = hydroxyl group), 2-thiophenmethanol (same as the synthesis apparatus 1) Tokyo Chemical Industry Co., Ltd.) 57.1 g (0.5 mol = sulfur atom) was weighed, the reaction time was 6 hours, and the addition amount of diethyl sulfate was changed to 0.4 g under the same conditions as in Synthesis Example 1. Reaction was performed. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1, and after confirming that 2-thiophenemethanol was not present in the system, the modified phenolic resin represented by chemical formula (1) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 3]
A phenol novolak resin (trade name: PSM4261, manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl group equivalent 107 g / eq) 53.5 g (0.5 mol = hydroxyl group), 2-thiophenmethanol (same as the synthesis apparatus 1) Under the same conditions as in Synthesis Example 1 except that 114.2 g (1.0 mol = sulfur atom) (manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed, the reaction time was 10 hours, and the addition amount of diethyl sulfate was changed to 0.6 g. Reaction was performed. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1, and after confirming that 2-thiophenemethanol was not present in the system, the modified phenolic resin represented by chemical formula (1) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 4]
A polyhydric phenol resin described in Japanese Patent Application Laid-Open No. 10-237060 was synthesized. Phenol (Tokyo Chemical Industry Co., Ltd.) 94.1 g (1 mol), Methanol (Tokyo Chemical Industry Co., Ltd.) 50 g, Sodium hydroxide (Tokyo Chemical Industry Co., Ltd.) 10 g (0.25 mol) Is charged into a glass reaction vessel equipped with a weighing, thermometer, dropping funnel, Dean-Stark moisture separator, reflux condenser, nitrogen inlet tube and stirring device, and the external temperature is raised to 100 ° C. under nitrogen flow. After the phenol was dissolved uniformly, when it was in a reflux state, 56.1 g (0.5 mol) of 2-thiophenecarboxydaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise in 2 hours and reacted for 50 hours. It was. After confirming that 2-thiophenecarboxydaldehyde does not exist in the system by gel permeation chromatography (model 830RI, JASCO Corporation) and gas chromatography (model GC-1700, manufactured by Shimadzu Corporation), neutralize with hydrochloric acid. 200 g of methyl isobutyl ketone was added, and after washing with water several times, unreacted phenol and methyl isobutyl ketone were distilled off under reduced pressure by heating, and then a polyhydric phenol resin represented by the following chemical formula (21) was replaced with SUS. It was made to discharge to the bat made of.

[Synthesis Example 5]
In the same reactor as in Synthesis Example 1, phenol dicyclopentadiene resin (trade name: DPR5000, manufactured by Mitsui Chemicals, Ltd., hydroxyl equivalent 180 g / eq) 72.0 g (0.4 mol = hydroxyl), 2-thiophenmethanol ( 22.8 g (0.2 mol = sulfur atom) manufactured by Tokyo Chemical Industry Co., Ltd. was weighed and reacted under the same conditions as in Synthesis Example 1. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1. After confirming that 2-thiophenemethanol was not present in the system, the modified phenolic resin represented by the chemical formula (5) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 6]
A phenol aralkyl resin (trade name: XLC-4L, manufactured by Mitsui Chemicals, Inc., hydroxyl group equivalent: 172 g / eq), 68.8 g (0.4 mol = hydroxyl group), 2-thiophenmethanol (same as in Synthesis Example 1) 11.4 g (0.1 mol) manufactured by Tokyo Chemical Industry Co., Ltd.),
The reaction was performed under the same conditions as in Synthesis Example 1 except that the reaction time was changed to 3 hours. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1, and after confirming that 2-thiophene methanol was not present in the system, the modified phenol resin represented by the chemical formula (9) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 7]
A phenol aralkyl resin (trade name: XLC-4L, manufactured by Mitsui Chemicals, Inc., hydroxyl group equivalent: 172 g / eq), 68.8 g (0.4 mol = hydroxyl group), 2-thiophenmethanol (same as in Synthesis Example 1) 22.8 g (0.2 mol = sulfur atom) manufactured by Tokyo Chemical Industry Co., Ltd. was weighed and reacted under the same conditions as in Synthesis Example 1. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1, and after confirming that 2-thiophene methanol was not present in the system, the modified phenol resin represented by the chemical formula (9) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 8]
In the same reactor as in Synthesis Example 1, phenol-aralkyl resin (trade name: XLC-4L, manufactured by Mitsui Chemicals, hydroxyl equivalent 172 g / eq) 68.8 g (0.4 mol = hydroxyl), 3-thiophenemethanol 22.8 g (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.2 mol = sulfur atom) was weighed and reacted under the same conditions as in Synthesis Example 1. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1. After confirming that 3-thiophenemethanol was not present in the system, the modified phenolic resin represented by the chemical formula (10) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 9]
A phenol aralkyl resin (trade name: XLC-4L, manufactured by Mitsui Chemicals, Inc., hydroxyl group equivalent: 172 g / eq), 68.8 g (0.4 mol = hydroxyl group), 2-thiophene ethanol (the same reactor as in Synthesis Example 1) Tokyo Chemical Industry Co., Ltd.) 25.6 (0.2 mol = sulfur atom) was weighed and reacted under the same conditions as in Synthesis Example 1. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1, and after confirming that 2-thiopheneethanol was not present in the system, the modified phenol resin represented by the chemical formula (11) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 10]
A phenol biphenyl aralkyl resin (trade name: MEH7851SS, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 230 g / eq) 69.0 g (0.3 mol = hydroxyl), 2-thiophenmethanol (Tokyo) Reaction was performed under the same conditions as in Synthesis Example 1 except that 3.4 g (0.03 mol = sulfur atom) (made by Kasei Kogyo Co., Ltd.) was weighed and the reaction time was changed to 2 hours. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1, and after confirming that 2-thiophene methanol was not present in the system, the modified phenol resin represented by chemical formula (13) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 11]
A phenol biphenyl aralkyl resin (trade name: MEH7851SS, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 230 g / eq) 69.0 g (0.3 mol = hydroxyl), 2-thiophenmethanol (Tokyo) Reaction was performed under the same conditions as in Synthesis Example 1 except that 8.6 g (0.075 mol = sulfur atom) (made by Kasei Kogyo Co., Ltd.) was weighed and the reaction time was changed to 3 hours. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1, and after confirming that 2-thiophene methanol was not present in the system, the modified phenol resin represented by chemical formula (13) was manufactured by SUS. It was discharged to the bat.

[Synthesis Example 12]
A naphthol aralkyl resin (trade name: α-NX-3.2, manufactured by Mitsui Chemicals, Inc., hydroxyl equivalent 218 g / eq), 65.4 g (0.3 mol = hydroxyl group), 2 -Thiophenemethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 17.1 g (0.15 mol = sulfur atom) was weighed and reacted under the same conditions as in Synthesis Example 1. Analysis was performed by gel permeation chromatography and gas chromatography in the same manner as in Synthesis Example 1, and after confirming that 2-thiophenemethanol was not present in the system, the modified phenolic resin represented by the chemical formula (17) was manufactured by SUS. It was discharged to the bat.

[Example 1]
44.5 g (0.29 g equivalent) of the modified phenol novolak resin (hydroxyl equivalent 155 g / eq) of Synthesis Example 1 as a curing agent and 2 g (2%) of triphenylphosphine as a curing accelerator were melt-kneaded at 140 ° C. for 10 minutes. After cooling to 100 ° C., 55.5 g (0.29 g equivalent) of biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resin Co., Ltd.), epoxy equivalent 193 g / eq) is added as an epoxy resin. did. A uniform resin composition was obtained by melt-kneading at 100 ° C. for 5 minutes.
Table 1 shows the evaluation results of the gel time and glass transition temperature (Tg) of this epoxy resin composition. Table 1 shows the results of evaluating the flexural modulus, flexural strength, moisture absorption, flame retardancy, and reflow resistance of the cured product of the epoxy resin composition.

[Example 2]
51.4 g (0.25 g equivalent) of a modified phenol novolak resin (hydroxyl equivalent 207 g / eq) of Synthesis Example 2 as a curing agent and a biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd.) as an epoxy resin The experiment was conducted in the same manner as in Example 1, except that the epoxy equivalent (193 g / eq) was changed to 48.6 g (0.25 g equivalent). The results are shown in Table 1.

[Example 3]
74.9 g (0.25 g equivalent) of the modified phenol novolac resin of Synthesis Example 3 as a curing agent and a biphenol type epoxy resin as an epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd.) The experiment was conducted in the same manner as in Example 1, except that the epoxy equivalent (193 g / eq) was changed to 48.6 g (0.25 g equivalent). The results are shown in Table 1.

[Comparative Example 1]
Phenol novolak resin (trade name: PSM4261, manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl group equivalent 107 g / eq) 35.7 g (0.33 g equivalent) as a curing agent and biphenol type epoxy resin (trade name: YX4000H) as an epoxy resin , Manufactured by Japan Epoxy Resin Co., Ltd.), and an epoxy equivalent of 193 g / eq) was changed to 64.3 g (0.33 g equivalent), and an experiment was conducted in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 2]
As a curing agent, 50.5 g (0.27 g equivalent) of the polyhydric phenol resin of Synthesis Example 4 (hydroxyl equivalent 189 g / eq) and a biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd.), The experiment was performed in the same manner as in Example 1 except that the epoxy equivalent (193 g / eq) was changed to 49.5 g (0.27 g equivalent). The results are shown in Table 2.

[Example 4]
54.4 g (0.24 g equivalent) of the modified phenol dicyclopentadiene resin (hydroxyl equivalent 228 g / eq) of Synthesis Example 5 as a curing agent and a biphenol type epoxy resin (trade name: YX4000H, Japan Epoxy Resins Co., Ltd.) as an epoxy resin Manufactured) and an epoxy equivalent of 193 g / eq) were replaced with 45.8 g (0.24 g equivalent). The results are shown in Table 1.

[Comparative Example 3]
Phenol dicyclopentadiene resin (trade name: DPR5000, manufactured by Mitsui Chemicals, Inc., hydroxyl group equivalent 180 g / eq) 48.3 g (0.27 g equivalent) as a curing agent and biphenol type epoxy resin (trade name: YX4000H) as an epoxy resin Experiments were conducted in the same manner as in Example 1 except that Japan Epoxy Resin Co., Ltd., epoxy equivalent 193 g / eq) was replaced with 51.7 g (0.27 g equivalent). The results are shown in Table 2.

[Example 5]
50.4 g (0.26 g equivalent) of the modified phenol aralkyl resin of Synthesis Example 6 as a curing agent (hydroxyl equivalent 196 g / eq) and a biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd.) as an epoxy resin The experiment was conducted in the same manner as in Example 1 except that the epoxy equivalent (193 g / eq) was changed to 49.4 g (0.26 g equivalent). The results are shown in Table 2.

[Example 6]
53.3 g (0.24 g equivalent) of a modified phenol aralkyl resin (hydroxyl equivalent 220 g / eq) of Synthesis Example 7 as a curing agent and a biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd.) as an epoxy resin The experiment was conducted in the same manner as in Example 1 except that the epoxy equivalent (193 g / eq) was changed to 46.7 g (0.24 g equivalent). The results are shown in Table 1.

[Example 7]
53.3 g (0.24 g equivalent) of a modified phenol aralkyl resin of Synthesis Example 8 as a curing agent and a biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd.) as an epoxy resin. The experiment was conducted in the same manner as in Example 1 except that the epoxy equivalent (193 g / eq) was changed to 46.7 g (0.24 g equivalent). The results are shown in Table 1.

[Example 8]
54.1 g (0.24 g equivalent) of the modified phenol aralkyl resin (hydroxyl equivalent 227 g / eq) of Synthesis Example 9 as a curing agent and a biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd.) as an epoxy resin The experiment was conducted in the same manner as in Example 1 except that the epoxy equivalent (193 g / eq) was changed to 45.9 g (0.24 g equivalent). The results are shown in Table 1.

[Comparative Example 4]
Phenol aralkyl resin (trade name: XLC-4L, manufactured by Mitsui Chemicals, Inc.)
Hydroxyl equivalent 172 g / eq) 47.1 g (0.27 g equivalent) and epoxy resin biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent 193 g / eq) 52.9 g (0 The experiment was conducted in the same manner as in Example 1 except that the amount was changed to .27 g equivalent). The results are shown in Table 2.

[Example 9]
46.8 g (0.20 g equivalent) of the modified phenol biphenyl aralkyl resin of Synthesis Example 10 as the curing agent (hydroxyl equivalent 240 g / eq), 1 g (1%) of triphenylphosphine as the curing accelerator, and biphenyl-aralkyl type epoxy as the epoxy resin The experiment was conducted in the same manner as in Example 1 except that the resin (trade name: NC3000, manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 273 g / eq) was changed to 53.2 g (0.20 g equivalent). The results are shown in the table.

[Example 10]
48.2 g (0.19 g equivalent) of the modified phenol biphenyl aralkyl resin (hydroxyl equivalent 254 g / eq) of Synthesis Example 11 as a curing agent, 1 g (1%) of triphenylphosphine as a curing accelerator, and biphenyl-aralkyl type epoxy as an epoxy resin An experiment was conducted in the same manner except that the resin (trade name: NC3000, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 273 g / eq) was replaced with 51.8 g (0.19 g equivalent). The results are shown in Table 1.

[Comparative Example 5]
Phenol biphenyl aralkyl resin (trade name: MEH7851SS, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 230 g / eq) 45.7 g (0.20 g equivalent) as a curing agent, and 1 g (1%) triphenylphosphine as a curing accelerator The same as Example 1 except that biphenyl-aralkyl type epoxy resin (trade name: NC3000, Nippon Kayaku Co., Ltd., epoxy equivalent 273 g / eq) was replaced with 54.3 g (0.20 g equivalent) as the epoxy resin. The experiment was conducted. The results are shown in Table 2.

[Example 11]
58.0 g (0.22 g equivalent) of the modified naphthol aralkyl resin of Synthesis Example 12 as a curing agent and a biphenol type epoxy resin (trade name: YX4000H, manufactured by Japan Epoxy Resins Co., Ltd.) as an epoxy resin The experiment was conducted in the same manner as in Example 1 except that the epoxy equivalent (193 g / eq) was changed to 42.0 g (0.22 g equivalent). The results are shown in Table 1.

[Comparative Example 6]
Naphthol aralkyl resin (trade name: α-NX-3.2, manufactured by Mitsui Chemicals, Ltd., hydroxyl equivalent 218 g / eq) 53.0 g (0.24 g equivalent) as a curing agent and biphenol type epoxy resin (epoxy resin) The experiment was conducted in the same manner as in Example 1 except that the product name: YX4000H, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 193 g / eq) was changed to 47.0 g (0.24 g equivalent). The results are shown in Table 2.

[Consideration of effects of invention]
The modified phenolic resin of the present invention has a structure in which a group represented by the general formula (1-1) is introduced as a side chain of an aromatic ring having a hydroxyl group, so that a conventional phenol novolak resin or a phenol aralkyl resin can be used. Adhesiveness and flame retardancy can be greatly enhanced without any loss of mechanical properties such as curability, glass transition temperature, hygroscopicity, and bending strength.

  The durability and moisture resistance time is 19 hours for the phenol novolac resin (Comparative Example 1), and 115 to 130 hours (Examples 1 to 3) for the modified phenol novolac resin of the present invention, and 91 for the phenol dicyclopentadiene resin (Comparative Example 3). With respect to time, the modified phenol dicyclopentadiene resin of the present invention is 149 hours (Example 4), the phenol aralkyl resin (Comparative Example 4) is 240 hours, and the modified phenol aralkyl resin of the present invention is 374 to 408 hours. (Examples 5 to 8), phenol biphenyl aralkyl resin (Comparative Example 5) is 276 hours, modified phenol biphenyl aralkyl resin of the present invention is 355 to 408 hours (Examples 9 and 10), naphthol aralkyl resin (Comparative) Example 6) for 206 hours, modified naphthol aralkyl tree of the invention In a 374 hours (Example 11), modified phenolic resins of the present invention has a very excellent effect on the durability humidity time compared to conventional phenolic resins.

Furthermore, flame retardancy is V-0 for the phenol novolak resin (Comparative Example 1) according to UL94 test evaluation criteria, while V-0 for the modified phenol novolac resin of the present invention and V- for the phenol aralkyl resin (Comparative Example 4). On the other hand, in the modified phenol aralkyl resin of the present invention, V-0 to V-1, the naphthol aralkyl resin (Comparative Example 6) is V-1, and in the modified naphthol aralkyl resin of the present invention, V-0 Example 11), and the modified phenolic resin of the present invention has excellent flame retardancy compared to conventional phenolic resins.

Moreover, the physical property value of the polymer obtained in the following Example and the comparative example was measured with the following method.
i) Glass transition temperature; Tg
The laminates produced in the examples and comparative examples were cut out and measured using a TMA device (Shimadzu TMA-50) in the compression mode under the following conditions. Load 10 g, constant speed load mode, measurement conditions 5 ° C./min, room temperature to 300 ° C., atmosphere nitrogen gas, flow rate 100 ml / min.
ii) Copper foil peel strength It was based on JIS C-6481 using the laminated board produced by the Example and the comparative example.
iii) Flame retardance Using the laminates produced in the examples and comparative examples, V determination was performed based on the flame retardancy test piece perpendicular to the flame test method UL94.
iv) Solder heat resistance The test piece was treated in a steam bath at 121 ° C. and a pressure of 2.0 atm for 3 hours, then immersed in 260 ° C. solder for 20 seconds (C-3 / 121/100), swollen, peeled off, etc. The presence or absence of an abnormality in the appearance was examined.
v) Content of hydroxyl group in phenolic resin The content of hydroxyl group in phenolic resin is determined by acetylating with pyridine as a solvent and acetic anhydride and decomposing the excess reagent with water. Determined by titration.

[Synthesis Example 13]
Phenol novolac resin (trade name: PSM4261, manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl group equivalent 107 g / eq) 53.5 g (0.5 mol = hydroxyl group), 2-thiophenmethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 28 0.5 g (0.25 mol = sulfur atom) was weighed, thermometer, dropping funnel, Dean-Stark moisture separator, reflux condenser, nitrogen inlet tube and a glass reaction vessel equipped with a stirring device, and under nitrogen flow The temperature was raised to 140 ° C. After confirming that it was uniformly melted while keeping the internal temperature at 140 ° C., 0.2 g of diethyl sulfuric acid was injected with a syringe. After completion of the injection, the reaction was carried out for 4 hours while separating and removing water generated at the same temperature. The change in molecular weight with time was measured by gel permeation chromatography (model 830RI, manufactured by JASCO Corporation), and the disappearance of 2-thiophene methanol was measured by gas chromatography (model GC-1700, manufactured by Shimadzu Corporation). After confirming the absence of 2-thiophene methanol, the modified phenolic resin represented by the chemical formula (A) was discharged into a SUS vat.

Sulfur was determined by quantitative analysis using an oxygen flask combustion method, and x, y, and z were determined from M / Z detected by field desorption ionization mass spectrometry. From these analysis results, it is found that the average number of repeating units n of the modified phenolic resin is 2.2, the sulfur content is 10.2%, and the total of x, y, and z is 3. It was.

[Synthesis Example 14]
In Synthesis Example 13, the same procedure as in Synthesis Example 1 was conducted except that the amount of 2-thiophene methanol was changed to 57.1 g, the reaction time was 6 hours, and the addition amount of diethyl sulfate was changed to 0.4 g. In the same manner as in Synthesis Example 13, the change in molecular weight with time was measured by gel permeation chromatography, and the disappearance of 2-thiophene methanol was measured by gas chromatography. After confirming the absence of 2-thiophene methanol in the system, the chemical formula The modified phenolic resin represented by (1) was discharged into a SUS vat.

From the results of quantitative analysis of sulfur and field desorption type ionization mass spectrometry, the average number of repeating units n is 2.1, the sulfur content is 15.1%, and the sum of x, y, and z is It was found to be 3.
[Synthesis Example 15]
A phenol aralkyl resin (trade name: XLC-4L, manufactured by Mitsui Chemicals, Inc., hydroxyl group equivalent: 172 g / eq), 68.8 g (0.4 mol = hydroxyl group), 2-thiophenmethanol (same as in Synthesis Example 1) 22.8 g (0.2 mol = sulfur atom) manufactured by Tokyo Chemical Industry Co., Ltd. was weighed and reacted under the same conditions as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the change in molecular weight with time was measured by gel permeation chromatography, and the disappearance of 2-thiophene methanol was measured by gas chromatography. After confirming the absence of 2-thiophene methanol in the system, the chemical formula The modified phenolic resin represented by (I) was discharged into a SUS vat.

From the results of quantitative analysis of sulfur and field desorption type ionization mass spectrometry, the average number of repeating units n is 3.4, the sulfur content is 6.3%, and the sum of x, y, and z is It was found to be 3.

[Example 12]
44.3 g (79.5 parts by weight, hydroxyl equivalent 1 with respect to epoxy equivalent 1) of the modified phenol novolak resin (hydroxyl equivalent 155 g / eq) obtained in Synthesis Example 13 as a curing agent, ortho-cresol novolac type as epoxy resin Epoxy resin (trade name: EOCN-102S, Nippon Kayaku Co., Ltd., epoxy equivalent 195 g / eq) 55.7 g (100 parts by weight), as a curing catalyst, 2.0 g of TPP (triphenylphosphine) 67 g of methyl ethyl ketone The varnish was prepared by dissolving in The gel time of the obtained varnish at 140 ° C. was 7 minutes. The varnish was impregnated into a glass substrate (Nittobo, 100 μm, E glass cloth) and dried at 140 ° C. for 5 minutes to obtain a prepreg. The obtained prepreg was tack-free and excellent in workability. 10 sheets of this prepreg are stacked, 18 μm thick electrolytic copper foil (made by Mitsui Metals) is stacked on both sides of the prepreg, laminated at a temperature of 175 ° C. and a molding pressure of 2.45 MPa for 2 hours, a resin content of 50%, a thickness of 1. A 2 mm double-sided copper-clad laminate was obtained.

[Example 13]
51.4 g (105.5 parts by weight, hydroxyl equivalent 1 with respect to epoxy equivalent 1) of the modified phenol novolak resin (hydroxyl equivalent 204 g / eq) of Synthesis Example 14 as a curing agent and ortho-cresol novolac type epoxy resin (epoxy equivalent) Product name: EOCN-102S, Nippon Kayaku Co., Ltd., epoxy equivalent 195 g / eq) was replaced with 48.6 g (100 parts by weight), and an experiment was conducted in the same manner as in Example 12. The results are shown in Table 3.

[Example 14]
47.8 g (91.6 parts by weight, hydroxyl equivalent 1 with respect to epoxy equivalent 1) of the modified phenol aralkyl resin (hydroxyl equivalent 220 g / eq) of Synthesis Example 15 as a curing agent and phenol aralkyl type epoxy resin (trade name) as an epoxy resin : E-XLC4L, manufactured by Mitsui Chemicals, Inc., epoxy equivalent 240 g / eq) was changed to 52.2 g (100 parts by weight) and the experiment was conducted in the same manner as in Example 12. The results are shown in Table 3.

[Comparative Example 7]
35.4 g (54.4 parts by weight, hydroxyl equivalent 1 with respect to epoxy equivalent 1) of phenol novolac resin (trade name: PSM-4261, manufactured by Gunei Chemical Co., Ltd., hydroxyl equivalent 107 g / eq) as a curing agent Example 12 except that ortho-cresol novolak type epoxy resin (trade name: EOCN-102S, Nippon Kayaku Co., Ltd., epoxy equivalent 195 g / eq) was replaced with 64.6 g (100 parts by weight) as an epoxy resin. The experiment was conducted in the same manner as above. The results are shown in Table 3.

[Comparative Example 8]
Phenol aralkyl resin (trade name: XLC-4L, manufactured by Mitsui Chemicals, Ltd., hydroxyl equivalent 172 g / eq) 41.7 g (71.5 parts by weight, hydroxyl equivalent 1 with respect to epoxy equivalent 1) and epoxy as a curing agent Experiment was conducted in the same manner as in Example 12 except that 58.3 g (100 parts by weight) of phenol aralkyl type epoxy resin (trade name: E-XLC4L, manufactured by Mitsui Chemicals, Inc., epoxy equivalent 240 g / eq) was used as the resin. Went. The results are shown in Table 3.

[Consideration on Examples and Comparative Examples]
The modified phenolic resin of the present invention has a structure in which a group represented by the general formula (1-2) is introduced as a side chain of an aromatic ring having a hydroxyl group, so that conventional phenol novolak resins and phenol aralkyl resins can be used. The thermophysical performance at the glass transition temperature possessed was not impaired at all, and the adhesion and flame retardancy performance could be greatly improved.
i) Copper peel strength (adhesion)
In Comparative Example 7, 14.1 N / cm, in Examples 12 and 13 using the modified phenol novolac resin of the present invention, 15.1 and 15.5 N / cm. Comparative Example 8 is 18.1 N / cm, whereas in Example 14 using the modified phenol aralkyl resin of the present invention, 18.1 N / cm. Therefore, when the modified phenolic resin of the present invention is used, the adhesiveness is extremely excellent as compared with the conventional phenolic resin.
ii) Flame retardance According to the UL94 test evaluation criteria, Comparative Example 7 was out of specification, whereas in Examples 12 and 13, V-1 and Comparative Example 8 were V-1. On the other hand, Example 14 is V-0 and has excellent flame retardancy.

An epoxy resin composition using the modified phenolic resin of the present invention as a curing agent, an epoxy resin cured product using the same, an insulating material for electrical / electronic components such as a semiconductor sealing material, and a laminated board such as a printed wiring board, Widely used in adhesives, molding materials, paints, etc.
In addition, the prepreg of the present invention in which a glass substrate is impregnated with an epoxy resin composition, a laminated board on which the prepreg is laminated, and an electronic circuit board using the laminated board are used for communication of home appliances, industrial machines, personal computers, mobile phones, etc. Widely used in printed wiring boards used in equipment, various control devices, automobiles, trains, airplanes, etc.

Claims (25)

A side chain of an aromatic ring having a hydroxyl group of a phenol resin which is an alternating copolymer of at least one phenol compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group is represented by the general formula (1- A modified phenolic resin, wherein the group represented by 1) is introduced .

(In the formula, R 1 represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms.)   The modified phenolic resin according to claim 1, comprising 0.01 to 2 moles of sulfur atoms with respect to 1 mole of hydroxyl group. The modified phenolic resin according to claim 1, wherein the modified phenolic resin is represented by the general formula (2-1).

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, or a linear chain having 1 to 10 carbon atoms. Or a branched or cyclic alkyl group or alkoxy group, which may be the same or different, the linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k, o, x and z are 0; (The integer of -4, m, and y show the integer of 0-3, the total number of x, y, and z shows the integer of 1-11. Moreover, the repeating unit number n shows the integer of 0-50.) The modified phenolic resin according to claim 1, wherein the modified phenolic resin is represented by the general formula (3-1).

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, or a linear chain having 1 to 10 carbon atoms. Or a branched or cyclic alkyl group or alkoxy group, which may be the same or different, the linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k, o, x and z are 0; The integer of -6, m, and y show the integer of 0-5, the total number of x, y, and z shows the integer of 1-17, and the repeating unit number n shows the integer of 0-50.) The modified phenolic resin according to claim 3, wherein the linking group A is at least one selected from a methylene group, a xylylene group, a biphenylaralkyl group, and a group represented by the following general formula (4-1).

The modified phenol resin according to claim 4, wherein the linking group A is at least one selected from a methylene group, a xylylene group, a biphenylaralkyl group, and a group represented by the following general formula (4-1).

The phenolic resin represented by the general formula (5-1) and the compound represented by the general formula (6-1) are reacted in the presence of an acid catalyst. The manufacturing method of the modified phenol resin represented by 2-1).

(Wherein R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, a linear or branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms, and may be the same or different. The linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k and o are integers of 0 to 4, m is an integer of 0 to 3, and the number of repeating units n is an integer of 0 to 50. .)

(In the formula, R ¹ represents a linear or branched or cyclic hydrocarbon group having 1 to 8 carbon atoms. B represents a hydroxyl group or a halogen atom.) The phenol resin represented by the general formula (7-1) and the compound represented by the general formula (6-1) according to claim 7 are reacted in the presence of an acid catalyst. The manufacturing method of the modified phenol resin represented by general formula (3-1) of description.

(Wherein R ² represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group, a linear or branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms, and may be the same or different. The linking group A represents a hydrocarbon group having 1 to 20 carbon atoms, k and o are integers of 0 to 6, m is an integer of 0 to 5, and the number of repeating units n is an integer of 0 to 50. .)   The modified phenolic resin according to claim 7, wherein the linking group A is at least one selected from a methylene group, a xylylene group, a biphenylaralkyl group and a group represented by the general formula (4-1) according to claim 5. Manufacturing method.   The modified phenol resin according to claim 8, wherein the linking group A is at least one selected from a methylene group, a xylylene group, a biphenylaralkyl group, and a group represented by the general formula (4-1) according to claim 6. Manufacturing method.   (A) An epoxy resin composition comprising a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin, (B) a curing agent, and (C) a curing accelerator, wherein the (B) curing agent is claimed. An epoxy resin composition comprising the modified phenolic resin according to any one of Items 1 to 6.   (D) The organic and / or inorganic filler is 100 to 1900 masses with respect to 100 mass parts of the total mass of the (A) bifunctional or higher functional epoxy compound or bifunctional or higher epoxy resin and the (B) curing agent. It contains in the range of a part, The epoxy resin composition of Claim 11 characterized by the above-mentioned.   The epoxy resin hardened | cured material formed by thermosetting the epoxy resin composition in any one of Claim 11 or Claim 12. (A) An epoxy resin composition containing a bifunctional or higher functional epoxy compound or a bifunctional or higher functional epoxy resin, (B) a curing agent, and (C) a curing accelerator, wherein the (B) curing agent is phenol, naphthol and a phenol resin is an alternating copolymer of a compound having at least one phenolic compound and a divalent linking group selected from derivatives thereof, and as a side chain of an aromatic ring having a hydroxyl group, the general formula (1 A prepreg, which is an epoxy resin composition which is a modified phenolic resin into which a group represented by -1) is introduced , wherein the glass base material is impregnated with the epoxy resin composition.

(In the formula, R ¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms.) The (B) curing agent is a phenol resin which is an alternating copolymer of at least one phenol compound selected from phenol, naphthol and derivatives thereof and a compound having a divalent linking group, and has a hydroxyl group. The prepreg according to claim 14, wherein the prepreg is a modified phenolic resin into which a group represented by the general formula (1-2) is introduced as a side chain of the ring.

(In the formula, R ¹ represents an alkylene group having 1 to 3 carbon atoms, a 1,4-cyclohexylene group, or a phenylene group.) The prepreg according to claim 15, wherein the (B) curing agent is a modified phenol resin represented by the general formula (2-2).

(In the formula, R ¹ represents an alkylene group having 1 to 3 carbon atoms, 1,4-cyclohexylene group, or phenylene group. R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a hydroxyl group, a phenyl group, Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which may be the same or different, and the linking group A is an alkylene group having 1 to 3 carbon atoms, a carbon atom; Represents a divalent group, a phenylene group, a xylylene group, or a biphenylaralkyl group of an alicyclic hydrocarbon of 6 to 12. k, o, x, and z are integers of 0 to 4, and m and y are 0 to 3 And the total number of x, y and z each represents an integer of 1 to 11. The number of repeating units n represents an integer of 0 to 50.) The prepreg according to claim 15, wherein the (B) curing agent is a modified phenol resin represented by the general formula (3-2).

(In the formula, R ¹ , R ² , the linking group A, k, o, x, z, m, y, and the number of repeating units n are the same as those in the general formula (2-2).) The linking group A is a modified phenol resin which is at least one selected from a methylene group, a xylylene group, a biphenylaralkyl group and a group represented by the following general formula (4-1). The prepreg as described.

The linking group A is a modified phenol resin which is at least one selected from a methylene group, a xylylene group, a biphenylaralkyl group and a group represented by the following general formula (4-1). The prepreg as described.

  The prepreg according to claim 14, wherein a glass substrate is impregnated with an epoxy resin composition having an epoxy equivalent of 170 to 1000 g / eq.   The prepreg according to claim 15, wherein a glass substrate is impregnated with an epoxy resin composition having an epoxy equivalent of 170 to 1000 g / eq.   (A) The glass substrate was impregnated with the epoxy resin composition in which the (B) curing agent was 2 to 150 parts by weight with respect to 100 parts by weight of the (A) bifunctional or higher functional epoxy compound or the bifunctional or higher functional epoxy resin. The prepreg according to claim 14.   (A) The glass substrate was impregnated with the epoxy resin composition in which the (B) curing agent was 2 to 150 parts by weight with respect to 100 parts by weight of the (A) bifunctional or higher functional epoxy compound or the bifunctional or higher functional epoxy resin. The prepreg according to claim 15.   A laminate obtained by laminating the prepreg according to any one of claims 14 to 23.   An electronic circuit board using the laminate according to claim 24.